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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Optical limiting properties of indium 5, 10, 15, 20-tetrakis (4-aminophenyl) porphyrin covalently linked to semiconductor quantum dots
- Authors: Managa, Muthumuni , Mgidlana, Sithi , Khene, Samson M , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186101 , vital:44463 , xlink:href="https://doi.org/10.1016/j.ica.2020.119838"
- Description: 5,10,15,20-tetrakis(4-aminophenyl) porphyrin and it indium derivative were synthesised and characterized then covalently linked to CdTe/ZnSe/ZnO semiconductor quantum dots. The nonlinear absorption of the complexes was studied using the Z-scan technique at 532 nm and 10 ns pulse in dimethyl sulfoxide. Indium 5,10,15,20- tetrakis(4-aminophenyl) porphyrin (InTAPP) exhibited the strongest nonlinear optical behaviour in comparison with the metal free derivative. DFT calculations were carried out using SDD basis set at B3LYP level of theory. The nonlinear absorption coefficient (βeff) values were determined experimentally using Z-scan whereby the first static hyperpolarizability (βHRS) value were determined using DFT calcutions.
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Photophysical and nonlinear optical properties of the positional isomers of 4-(4-tertbutylphenoxy) substituted cobalt, nickel and copper phthalocyanines
- Authors: Neduvhuledza, Zelda , Nkaki, Thabo , Louzada, Marcel , Nyokong, Tebello , Khene, Samson M
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186067 , vital:44460 , xlink:href="https://doi.org/10.1016/j.optmat.2020.110195"
- Description: This paper reports on the third order nonlinear optical properties of cobalt, nickel and tetrakis(4- terbutylphenoxy)phthalocyaninatocopper(II) isomers, using the Z-scan technique. Metal-free isomers were found to have high nonlinear absorption coefficient (β) values compared to the metalated isomers. Metal-free C2v isomer was found to have the highest β value of 1.52 × 10− 10 mMW− 1 in THF. All the metal-free and metal phthalocyanine isomers nonlinear properties were found to be dependent on the singlet state absorption. Imaginary second order nonlinear hyperpolarizability (Im[γ]), ground state cross section (σg), excited states cross sections (σs and σt) and two photon absorption (TPA) cross section (σTPA) values are reported in this work. The five-energy level model rate equations were used to model the nonlinear response and absorption cross sections.
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Nonlinear optical properties of metal free and nickel binuclear phthalocyanines
- Authors: Kabwe, Kapambwe P , Louzada, Marcel , Britton, Jonathan , Olomola, Temitope O , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186846 , vital:44539 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.05.003"
- Description: This work employs the open and closed Z-scan aperture technique to comparatively study the nonlinear optical (NLO) properties of nickel and metal free 4-tert-butylphenoxy phthalocyanine, biphenyl bridged bis-4-tert-butylphenoxy phthalocyanine and naphthalene bridged bis-4-tert-butylphenoxy phthalocyanine. Density functional theory (DFT) calculations of dipolar and octupolar ( J=1 and J=3) contribution were determined theoretically from hyper-Rayleigh scattering (HRS) response ( HRS) values.
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Photophysical and nonlinear optical characteristics of pyridyl substituted phthalocyanine-detonation nanodiamond conjugated systems in solution
- Authors: Matshitse, Refilwe , Khene, Samson M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187079 , vital:44563 , xlink:href="https://doi.org/10.1016/j.diamond.2019.03.013"
- Description: In this study photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-phthalocyanine nanoconjugate systems containing: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (H2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato zinc(II) (ZnTPPc) and 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato silicon(IV) hydroxide (Si(OH)2TPPc), were investigated in dimethylsulfoxide solution. Pcs were non-covalently linked to nanondiamonds (also covalently linked for Si(OH)2TPPc) and investigated using 532 nm laser excitation at 10 ns pulses for their optical limiting properties. Complexes that have higher triplet state absorption also possessed enhanced nonlinear optical behaviour following reverse saturable absorption mechanism. Superior optical performance is observed when the Pcs had a central metal with axial ligands conjugated to DNDs in solution. Nanoconjugate of DNDs-Si(OH)2TPPc and respective Pc in solution gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 2.91 × 10−8 and 3.17 × 10−8 esu and 3.88 × 10−28 and 4.22 × 10−28 esu, respectively, with Ilim value of 0.47 and 0.39 J·cm−2.
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Spectroscopic and nonlinear optical properties of alkyl thio substituted binuclear phthalocyanines
- Authors: Makinde, Zainab O , Louzada, Marcel S , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187485 , vital:44661 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.10.022"
- Description: This work presents the spectroscopic and nonlinear optical properties of metal free binuclear and monomeric 4- (pentylthio)phthalocyanine and cobalt 4,5-(bipentylthio)phthalocyanine. Second order nonlinear absorption coefficient (β) values for the complexes were determined and compared.
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Photophysics and NLO properties of Ga (III) and In (III) phthalocyaninates bearing diethyleneglycol chains
- Authors: Managa, Muthumuni , Khene, Samson M , Britton, Jonathan , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Y , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/237822 , vital:50556 , xlink:href="https://doi.org/10.1142/S1088424618500128"
- Description: This work reports on synthesis and characterizations of Ga(III) and In(III) complexes, formed by 2,3-bis[2′′-(2′′′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxy phthalocyanine (1H2) coordinating acetatoindium(III) (1InOAc) and hydroxogallium(III) (1GaOH) Photophysical properties of hydroxogallium(III) phthalocyaninate 1GaOH and acetatoindium(III) phthalocyaninate 1InOAc were studied by UV-vis, fluorescence spectroscopy and time-resolved methods. The nonlinear absorption of the complexes was studied using the Z-scan technique at 532 nm and 10 ns pulse in DMSO and in thin films formed by composite with poly(bisphenol A carbonate) — PBC. The magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work showed that complex 1InOAc exhibited the strongest nonlinear optical behavior in comparison with 1GaOH in solution and a reverse tendency when embedded in PBC thin films. DFT calculations were used to rationalize these results.
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The effect of the cobalt and manganese central metal ions on the nonlinear optical properties of tetra (4-propargyloxyphenoxy) phthalocyanines
- Authors: Mwanza, Daniel , Louzada, Marcel , Britton, Jonathan , Sekhosana, Kutloano E , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233357 , vital:50083 , xlink:href="https://doi.org/10.1039/C8NJ00748A"
- Description: The metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (Mn(OAc)TPrOPhOPc) tetra propargyloxyphenoxy phthalocyanines were evaluated for their potential as optical limiting materials. The effect of the substituents and the central metal ions on the nonlinear optical properties was evaluated. The metal-free phthalocyanine exhibited better nonlinear optical properties when compared to the cobalt and manganese complexes owing to the metal ions quenching the excited state due to their half-filled d-orbitals. The nonlinear absorption coefficient (βeff, ×10−5 m MW−1) followed the trend of H2TPrOPhOPc > CoTPrOPhOPc > Mn(OAc)TPrOPhOPc. The values βeff (×10−5 m MW−1) using 532 nm Nd:YAG (560 nm monochromatic Ekspla) laser sources were 23.5 > 14.3 > 9.20 (14.4). The second-order nonlinear coefficient obtained using density functional theory calculations, the theoretical hyper-Rayleigh scattering (βHRS, ×10−28 esu), showed the decreasing trend for H2TPrOPhOPc (2.28) > CoTPrOPhOPc (2.10) > Mn(OAc)TPrOPhOPc (1.86). The 4-(propargyloxy)phenoxy substituents enhanced the optical limiting properties of the synthesized phthalocyanines.
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Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol
- Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
- Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
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Exploiting Click Chemistry for the Covalent Immobilization of Tetra (4-Propargyloxyphenoxy) Metallophthalocyanines onto Phenylazide-Grafted Gold Surfaces
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
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Improved nonlinear optical behaviour of ball type indium (III) phthalocyanine linked to glutathione capped nanoparticles
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
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Solvent effect on the third-order nonlinear optical properties of α-and β-tertbutyl phenoxy-substituted tin (IV) chloride phthalocyanines
- Authors: Louzada, Marcel , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188910 , vital:44797 , xlink:href="https://doi.org/10.1021/acs.jpca.7b07349"
- Description: This paper investigates the third-order nonlinear optical properties of 4α-(4-tert-butylphenoxy) phthalocyaninato dichlorotin(IV) (α-SnOtBpPc) and 4β-(4-tert-butylphenoxy) phthalocyaninato dichlorotin(IV) (β-SnOtBpPc) in different organic solvents. The third-order susceptibilities of α-SnOtBpPc and βSnOtBpPc are reported in different solvents, using Z-scan techniques with 10 ns laser pulses at 532 nm. Their nonlinear absorption coefficient and absorption cross sections were also determined. The molecular imaginary components of the secondorder hyperpolarizability Im[γ] of α-SnOtBpPc and β-SnOtBpPc were found to be 2.60 × 10−31 and 2.94 × 10−31 esu (tetrahydrofuran), 2.12 × 10−31 and 2.54 × 10−31 esu (chloroform), 3.06 × 10−31 and 2.54 × 10−31 esu (dichloromethane), and 1.27 × 10−31 and 1.50 × 10−31 esu (toluene), respectively. This study found that substitution at the α position has an effect of lowering the two-photon (2PA) cross section value for α-SnOtBpPc compared to that for β-SnOtBpPc, with values of 64.30 and 456.65 GM, respectively. The large 2PA cross section observed in β-SnOtBpPc is attributed to the decreased energy difference between the virtual state and the LUMO.
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Synthesis, photophysical and nonlinear optical behavior of neodymium based trisphthalocyanine
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith K , Khene, Samson M , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241412 , vital:50937 , xlink:href="https://doi.org/10.1016/j.ica.2014.11.029"
- Description: Tris-{1(4),8(11),15(18),22(25)-tetra(4-tertbutylphenoxy) phthalocyaninato} dineodymium (III) was synthesised and its nonlinear optical and fluorescence behavior was studied. Low fluorescence quantum yield (ФF = 0.03) was obtained with a fluorescence lifetime τF = 4.31 ns for this complex. Nonlinear optical parameters for the complex were determined using the Z-scan technique and the values of Im[χ(3)] and γ were of the order of 10−10 and 10−28 esu, respectively. Square wave voltammetry revealed three reduction and two oxidation couples for the complex.
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Effects of redox mediators on the catalytic activity of iron porphyrins towards oxygen reduction in acidic media
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated.
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Enhanced optical limiting performance in phthalocyanine-quantum dot nanocomposites by free-carrier absorption mechanism
- Authors: Sanusi, Kayode , Khene, Samson M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193904 , vital:45404 , xlink:href="https://doi.org/10.1016/j.optmat.2014.07.024"
- Description: Enhanced nonlinear optical properties (in dimethyl sulphoxide) is observed for 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (InPc) when covalently linked to CdSe/ZnS or CdSe quantum dots (QDs). The experimental nonlinear optical parameters were obtained from Z-Scan measurements. Contributions from two-photon absorption (2PA) due to the InPc, and free-carrier absorption (FCA) by QDS have been identified as the main factors responsible for the enhanced optical limiting. The effective nonlinear absorption coefficient for InPc-CdSe/ZnS was found to be 700.0 cm/GW. The FCA cross-sections for InPc-CdSe/ZnS and InPc-CdSe composites were found to be 1.52 × 10−19 and 6.00 × 10−20 cm2 respectively. A much lower limiting threshold of 92 mJ cm−2 was observed for InPc-CdSe/ZnS nanocomposite, hence, making it suitable for use as optical limiting material. Density Functional Theory (DFT) calculations on similar phthalocyanine-quantum dots system was modeled in order to explain the enhancement in the observed nonlinear optical properties of the Pc in the presence of the QDs. The experimentally determined nonlinear optical properties are well within the range of the DFT calculated properties.
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Fluorescence behavior of glutathione capped CdTe@ ZnS quantum dots chemically coordinated to zinc octacarboxy phthalocyanines
- Authors: Sekhosana, Kutloano E , Antunes, Edith M , Khene, Samson M , D'Souza, Sarah , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242019 , vital:50993 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.11.044"
- Description: Core–shell CdTe@ZnS quantum dots capped with glutathione (CdTe@ZnS–GSH) were covalently linked to zinc octacarboxy phthalocyanine (ZnPc(COOH)8). The conjugate was characterized by UV/Vis, infrared and X-Ray photoelectron spectroscopies as well as transmission electron and atomic force microscopies. The fluorescence quantum yields of the core CdTe capped with thioglycolic acid increased upon formation of the core-shell. Upon conjugation with ZnPc(COOH)8, the fluorescence quantum yield of CdTe@ZnS–GSH decreased due to energy transfer from the latter to the Pc. The average fluorescence lifetime of the CdTe@ZnS–GSH QD also decreased upon conjugation from 26.2 to 13.3 ns.
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Fluorescence “switch on” of conjugates of CdTe@ ZnS quantum dots with Al, Ni and Zn tetraamino-phthalocyanines by hydrogen peroxide
- Authors: Adegoke, Oluwasesan , Khene, Samson M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241750 , vital:50966 , xlink:href="https://doi.org/10.1007/s10895-013-1222-x"
- Description: In this study, we have developed a novel nanoprobe for H2O2 based on the conjugation of CdTe@ZnS quantum dots (QDs) to different metal tetraamino-phthalocyanine (MTAPc): (M = (OAc)Al, {OAc = acetate}, Ni and Zn). Chemical coordination of the QDs to the MTAPc resulted in the fluorescence “switch off” of the linked QDs which was associated with Förster resonance energy transfer (FRET). In the presence of varying concentration of H2O2, the fluorescence of the linked QDs was progressively “switched on” and the FRET mechanism between the QDs and the MTAPc was disrupted. The sensitivity/limit of detection of the nanoprobe followed the order: QDs-ZnTAPc (2.2 μM) > QDs-NiTAPc (4.4 μM) > QDs-AlTAPc (9.8 μM) while the selectivity followed the order: QDs-NiTAPc > QDs-AlTAPc > QDs-ZnTAPc. The varying degree of sensitivity/selectivity and mechanism of detection is discussed in detail.
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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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Third order nonlinear optical properties of phthalocyanines in the presence nanomaterials and in polymer thin films
- Authors: Britton, Jonathan , Durmus, Mahmut , Khene, Samson M , Chauke, Vongani , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241772 , vital:50968 , xlink:href="https://doi.org/10.1142/S108842461350003X"
- Description: Third order nonlinear optical properties were determined for phthalocyanine complexes 1–10 containing In, Ga and Zn central metals and tetra- or octa-substituted with benzyloxyphenoxy, phenoxy, tert-butylphenoxy and amino groups at peripheral or non-peripheral positions. The phthalocyanines were embedded in poly (methyl methacrylate) polymer in the presence of CdTe quantum dots. All complexes 1–10 were studied in the presence of CdTe quantum dots and embedded in poly (methyl methacrylate) to form thin films. Complex 3 tetrasubstituted with tert-butylphenoxy groups at non-peripheral positions was also studied in the presence of CdS, CdSe quantum dots, fullerenes, single walled carbon nanotubes. Third order nonlinear optical parameters generally increase for Pcs in the presence of CdTe quantum dots.
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Photooxidation of 4-chlorophenol sensitized by lutetium tetraphenoxy phthalocyanine anchored on electrospun polystyrene polymer fiber
- Authors: Zugle, Ruphino , Antunes, Edith M , Khene, Samson M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245787 , vital:51405 , xlink:href="https://doi.org/10.1016/j.poly.2011.11.005"
- Description: An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.
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