Development of Graphene/CdSe Quantum Dots-Co Phthalocyanine Nanocomposite for Oxygen Reduction Reaction
- Nyoni, Stephen, Nyokong, Tebello
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7300 , http://hdl.handle.net/10962/d1020368
- Description: Nanocomposites containing CdSe quantum dots, tetra(4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II)) (CoPyPc) and reduced graphene nanosheets (rGNS) were devoloped and used for the modification of a glassy carbon electrode. Characterization of the nanocomposites was done by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses. Cyclic voltammetry (CV) was used for electrochemical characterization of the prepared nanocomposite for oxygen reduction reaction. The oxygen reduction activity for rGNS/CdSe-CoPyPc nanocomposite was found to be superior over the individual nanomaterials in this study. The activity of the nanocomposite towards oxygen reduction was also tested for tolerance to methanol crossover effect using chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) studies. , Original publication is available at http://dx.doi.org/10.1002/elan.201400372
- Full Text: false
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7300 , http://hdl.handle.net/10962/d1020368
- Description: Nanocomposites containing CdSe quantum dots, tetra(4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II)) (CoPyPc) and reduced graphene nanosheets (rGNS) were devoloped and used for the modification of a glassy carbon electrode. Characterization of the nanocomposites was done by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses. Cyclic voltammetry (CV) was used for electrochemical characterization of the prepared nanocomposite for oxygen reduction reaction. The oxygen reduction activity for rGNS/CdSe-CoPyPc nanocomposite was found to be superior over the individual nanomaterials in this study. The activity of the nanocomposite towards oxygen reduction was also tested for tolerance to methanol crossover effect using chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) studies. , Original publication is available at http://dx.doi.org/10.1002/elan.201400372
- Full Text: false
Effect of bovine serum albumin and single walled carbon nanotube on the photophysical properties of zinc octacarboxy phthalocyanine
- Ogbodu, Racheal O, Nyokong, Tebello
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7321 , http://hdl.handle.net/10962/d1020566
- Description: This work reports on the photophysical parameters of the conjugate between zinc octacarboxy phthalocyanine (ZnOCPc) and bovine serum albumin (BSA) represented as ZnOCPc–BSA (1) which was further adsorbed onto single walled carbon nanotubes (SWCNT) represented as (ZnOCPc–BSA–SWCNT 2). ZnOCPc (without BSA) was also adsorbed on SWCNT represented as ZnOCPc–SWCNT (3). The presence of BSA resulted in the increase in singlet oxygen quantum yield (ΦΔ) for 1 (at ΦΔ = 0.44) and 2 (at ΦΔ = 0.41) compared to ΦΔ = 0.21 for ZnOCPc alone. For complex 3 which did not contain BSA singlet oxygen quantum yield decreased. , Original publication is available at http://dx.doi.org/10.1016/j.saa.2013.10.064
- Full Text: false
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7321 , http://hdl.handle.net/10962/d1020566
- Description: This work reports on the photophysical parameters of the conjugate between zinc octacarboxy phthalocyanine (ZnOCPc) and bovine serum albumin (BSA) represented as ZnOCPc–BSA (1) which was further adsorbed onto single walled carbon nanotubes (SWCNT) represented as (ZnOCPc–BSA–SWCNT 2). ZnOCPc (without BSA) was also adsorbed on SWCNT represented as ZnOCPc–SWCNT (3). The presence of BSA resulted in the increase in singlet oxygen quantum yield (ΦΔ) for 1 (at ΦΔ = 0.44) and 2 (at ΦΔ = 0.41) compared to ΦΔ = 0.21 for ZnOCPc alone. For complex 3 which did not contain BSA singlet oxygen quantum yield decreased. , Original publication is available at http://dx.doi.org/10.1016/j.saa.2013.10.064
- Full Text: false
Effects of analytes on the fluorescence properties of CdTe@ZnS quantum dots decorated with cobalt tetraamino-phthalocyanine
- Adegoke, Oluwasesan, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7315 , http://hdl.handle.net/10962/d1020541
- Description: In this work, we have carried out an investigation on the effects of different biologically active analytes on the fluorescence response of glutathione-capped CdTe@ZnS quantum dots (QDs)-colbalt tetraamino-phthalocyanine nanoconjugate system. Firstly, fluorescence quenching occurred. Experimental results showed that some analytes either “turned on”, others further quenched or showed no effect on the fluorescence emission of the nanoprobe. , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2013.09.079
- Full Text: false
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7315 , http://hdl.handle.net/10962/d1020541
- Description: In this work, we have carried out an investigation on the effects of different biologically active analytes on the fluorescence response of glutathione-capped CdTe@ZnS quantum dots (QDs)-colbalt tetraamino-phthalocyanine nanoconjugate system. Firstly, fluorescence quenching occurred. Experimental results showed that some analytes either “turned on”, others further quenched or showed no effect on the fluorescence emission of the nanoprobe. , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2013.09.079
- Full Text: false
Effects of differently shaped silver nanoparticles on the photophysics of pyridylsulfanyl-substituted phthalocyanines
- D’Souza, Sarah, Mashazi, Philani N, Britton, Jonathan, Nyokong, Tebello
- Authors: D’Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7290 , http://hdl.handle.net/10962/d1020353
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.06.038
- Full Text: false
- Authors: D’Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7290 , http://hdl.handle.net/10962/d1020353
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.06.038
- Full Text: false
Effects of number of ring substituents on the physicochemical properties of zinc aminophenoxy phthalocyanine-single walled carbon nanotube conjugate
- Ogbodu, Racheal O, Nyokong, Tebello
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7319 , http://hdl.handle.net/10962/d1020564
- Description: This work reports on the linking of zinc monoaminophenoxy (ZnMAPPc) or zinc tetraaminophenoxy phthalocyanine (ZnTAPPc) complexes to single walled carbon nanotubes (SWCNTs) through either covalent or non-covalent (adsorption) bonding. The functionalized complexes showed better thermal stability when compared to the SWCNT-COOH, ZnMAPPc and ZnTAPPc alone as confirmed by thermogravimetric analyses. The covalently linked ZnMAPc-SWCNT showed higher electron transfer rate constant and photoinduced electron efficiency when compared to adsorbed complexes. ZnMAPPc-SWCNT complexes (linked and adsorbed) showed better photophysical and photochemical properties when compared to ZnTAPPc-SWCNT complexes. The triplet, singlet oxygen and florescence quantum yields of ZnMAPPc (or ZnTAPPc) decrease upon linking or adsorption onto SWCNTs. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2013.09.015
- Full Text: false
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7319 , http://hdl.handle.net/10962/d1020564
- Description: This work reports on the linking of zinc monoaminophenoxy (ZnMAPPc) or zinc tetraaminophenoxy phthalocyanine (ZnTAPPc) complexes to single walled carbon nanotubes (SWCNTs) through either covalent or non-covalent (adsorption) bonding. The functionalized complexes showed better thermal stability when compared to the SWCNT-COOH, ZnMAPPc and ZnTAPPc alone as confirmed by thermogravimetric analyses. The covalently linked ZnMAPc-SWCNT showed higher electron transfer rate constant and photoinduced electron efficiency when compared to adsorbed complexes. ZnMAPPc-SWCNT complexes (linked and adsorbed) showed better photophysical and photochemical properties when compared to ZnTAPPc-SWCNT complexes. The triplet, singlet oxygen and florescence quantum yields of ZnMAPPc (or ZnTAPPc) decrease upon linking or adsorption onto SWCNTs. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2013.09.015
- Full Text: false
Electrocatalytic behahiour of cobalt tetraamino-phthalocyanine in the presence of a composite of reduced graphene nanosheets and of multi-walled carbon nanotubes
- Nyoni, Stephen, Nyokong, Tebello
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7309 , http://hdl.handle.net/10962/d1020386
- Description: A composite of multi-walled carbon nanotubes (MWCNT) with reduced graphene nanosheets (rGNS-2) was developed in order to minimize the restacking of the latter. The composite was used to modify a glassy carbon electrode (GCE). GCE was further modified with cobalt tetraamino phthalocyanine (CoTAPc). The modified electrode is represented as rGNS-2-MWCNT-CoTAPc-GCE. X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electrochemical microscopy and Raman spectroscopy were used to explore into surface functionalities, morphology and topography of the nanocomposite. The rGNS-2-MWCNT-CoTAPc-GCE had a low limit of detection of 3.32 × 10−8 M towards the detection of paraguat as a test analyte. A mechanism for paraquat detection using an rGNS-2-MWCNT-CoTAPc-GCE is also proposed in this work. , Original publication is available at http://dx.doi.org/10.1016/j.electacta.2014.05.093
- Full Text: false
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7309 , http://hdl.handle.net/10962/d1020386
- Description: A composite of multi-walled carbon nanotubes (MWCNT) with reduced graphene nanosheets (rGNS-2) was developed in order to minimize the restacking of the latter. The composite was used to modify a glassy carbon electrode (GCE). GCE was further modified with cobalt tetraamino phthalocyanine (CoTAPc). The modified electrode is represented as rGNS-2-MWCNT-CoTAPc-GCE. X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electrochemical microscopy and Raman spectroscopy were used to explore into surface functionalities, morphology and topography of the nanocomposite. The rGNS-2-MWCNT-CoTAPc-GCE had a low limit of detection of 3.32 × 10−8 M towards the detection of paraguat as a test analyte. A mechanism for paraquat detection using an rGNS-2-MWCNT-CoTAPc-GCE is also proposed in this work. , Original publication is available at http://dx.doi.org/10.1016/j.electacta.2014.05.093
- Full Text: false
Electrochemical behaviour of gold nanoparticles and Co tetraaminophthalocyanine on glassy carbon electrode
- Maringa, Audacity, Antunes, Edith M, Nyokong, Tebello
- Authors: Maringa, Audacity , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7306 , http://hdl.handle.net/10962/d1020383
- Description: We report on the electrodeposition of gold nanoparticles (AuNPs) onto the glassy carbon electrode (GCE) followed by polymerization of cobalt tetraamino phthalocyanine (CoPc(NH2)4) on top (represented as poly-CoPc(NH2)4-/AuNPs-GCE). The modified electrode where CoPc(NH2)4 is polymerized first followed by deposition of AuNPs is represented as AuNPs/poly-CoPc(NH2)4-GCE. In the absence of AuNPs, the electrode is represented as poly-CoPc(NH2)4-GCE or for AuNPs alone (AuNPs-GCE). The surface coverage was 1.5 × 10−9 mol cm−2 for AuNPs-GCE and 3.0 × 10−9 mol cm−2 for the rest of the modified electrodes. AuNPs/CoPc(NH2)4-GCE exhibited high electrocatalytic activity towards the oxidation of nitrite, with detection potential of 0.76 V. The catalytic rate constant of 3.96 × 107 cm3 mol−1 s−1 was obtained for nitrite oxidation. , Original publication is available at http://dx.doi.org/10.1016/j.electacta.2013.12.132
- Full Text: false
- Authors: Maringa, Audacity , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7306 , http://hdl.handle.net/10962/d1020383
- Description: We report on the electrodeposition of gold nanoparticles (AuNPs) onto the glassy carbon electrode (GCE) followed by polymerization of cobalt tetraamino phthalocyanine (CoPc(NH2)4) on top (represented as poly-CoPc(NH2)4-/AuNPs-GCE). The modified electrode where CoPc(NH2)4 is polymerized first followed by deposition of AuNPs is represented as AuNPs/poly-CoPc(NH2)4-GCE. In the absence of AuNPs, the electrode is represented as poly-CoPc(NH2)4-GCE or for AuNPs alone (AuNPs-GCE). The surface coverage was 1.5 × 10−9 mol cm−2 for AuNPs-GCE and 3.0 × 10−9 mol cm−2 for the rest of the modified electrodes. AuNPs/CoPc(NH2)4-GCE exhibited high electrocatalytic activity towards the oxidation of nitrite, with detection potential of 0.76 V. The catalytic rate constant of 3.96 × 107 cm3 mol−1 s−1 was obtained for nitrite oxidation. , Original publication is available at http://dx.doi.org/10.1016/j.electacta.2013.12.132
- Full Text: false
Enhanced nonlinear optical properties of octa-substituted lead and cadmium phthalocyanines when embedded in poly(bisphenol A carbonate) as thin films
- Mkhize, Colin, Britton, Jonathan, Nyokong, Tebello
- Authors: Mkhize, Colin , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7320 , http://hdl.handle.net/10962/d1020565
- Description: This work presents photophysical and nonlinear optical properties of a novel Cd 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (CdOtBPPc) and compare them with those of Pb 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (PbOtBPPc). For both the CdOtBPPc and PbOtBPPc, third order imaginary susceptibility and second order hyperpolarizability values were found to be within the limit set for good optical limiters. The Pcs were embedded in poly (methyl methacrylate) (PMMA) and poly(bisphenol A carbonate) (PBC) as thin films. The optical limiting values of the Pcs once embedded in film were found to be greatly improved and the limiting fluence of each film was well below the maximum threshold. Both PbOtBPPc and CdOtBPPc showed better optical limiting when embedded in PBC compared to PMMA. CdOtBPPc shows better nonlinear optical behavior than PbOtBPPc in solution and as thin films, even though the former is aggregated in solution. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.07.025
- Full Text: false
- Authors: Mkhize, Colin , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7320 , http://hdl.handle.net/10962/d1020565
- Description: This work presents photophysical and nonlinear optical properties of a novel Cd 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (CdOtBPPc) and compare them with those of Pb 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (PbOtBPPc). For both the CdOtBPPc and PbOtBPPc, third order imaginary susceptibility and second order hyperpolarizability values were found to be within the limit set for good optical limiters. The Pcs were embedded in poly (methyl methacrylate) (PMMA) and poly(bisphenol A carbonate) (PBC) as thin films. The optical limiting values of the Pcs once embedded in film were found to be greatly improved and the limiting fluence of each film was well below the maximum threshold. Both PbOtBPPc and CdOtBPPc showed better optical limiting when embedded in PBC compared to PMMA. CdOtBPPc shows better nonlinear optical behavior than PbOtBPPc in solution and as thin films, even though the former is aggregated in solution. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.07.025
- Full Text: false
Improved l-cysteine electrocatalysis through a sequential drop dry technique using multi-walled carbon nanotubes and cobalt tetraaminophthalocyanine conjugates
- Nyoni, Stephen, Mugadza, Tawanda, Nyokong, Tebello
- Authors: Nyoni, Stephen , Mugadza, Tawanda , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7308 , http://hdl.handle.net/10962/d1020385
- Description: Voltammetry, chronoamperometry, scanning electrochemical microscopy and electrochemical impedance spectroscopy methods are used for characterization of a glassy carbon electrode modified with multi-walled carbon nanotubes (MWCNTs)–cobalt tetraaminophthalocyanine (CoTAPc) mixture or sequential drop dry modification technique whereby the MWCNTs are first placed on to the electrode followed by CoTAPc. The sequential drop dry CoTAPc–MWCNTs modified surface gave better catalytic responses with a catalytic rate constant of 2.2 × 105 M−1 s−1, apparent electron transfer rate constant of 0.073 cm s−1, and a limit of detection of 2.8 × 10−7 M. Scanning electrochemical microscopy (SECM) surface characterization (topography and reactivity) further gave proof the better catalytic perfomance of the sequential drop dry CoTAPc–MWCNTs modified surface. , Original publication is available at http://dx.doi.org/10.1016/j.electacta.2013.10.023
- Full Text: false
- Authors: Nyoni, Stephen , Mugadza, Tawanda , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7308 , http://hdl.handle.net/10962/d1020385
- Description: Voltammetry, chronoamperometry, scanning electrochemical microscopy and electrochemical impedance spectroscopy methods are used for characterization of a glassy carbon electrode modified with multi-walled carbon nanotubes (MWCNTs)–cobalt tetraaminophthalocyanine (CoTAPc) mixture or sequential drop dry modification technique whereby the MWCNTs are first placed on to the electrode followed by CoTAPc. The sequential drop dry CoTAPc–MWCNTs modified surface gave better catalytic responses with a catalytic rate constant of 2.2 × 105 M−1 s−1, apparent electron transfer rate constant of 0.073 cm s−1, and a limit of detection of 2.8 × 10−7 M. Scanning electrochemical microscopy (SECM) surface characterization (topography and reactivity) further gave proof the better catalytic perfomance of the sequential drop dry CoTAPc–MWCNTs modified surface. , Original publication is available at http://dx.doi.org/10.1016/j.electacta.2013.10.023
- Full Text: false
Optical nonlinearities and photophysicochemical behaviour of green and blue forms of lutetium bisphthalocyanines
- Sekhosana, Kutloano Edward, Amuhaya, Edith, Mack, John, Nyokong, Tebello
- Authors: Sekhosana, Kutloano Edward , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7316 , http://hdl.handle.net/10962/d1020543
- Description: A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications. , Original publication is available at http://dx.doi.org/10.1039/C4TC00505H
- Full Text:
- Authors: Sekhosana, Kutloano Edward , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7316 , http://hdl.handle.net/10962/d1020543
- Description: A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications. , Original publication is available at http://dx.doi.org/10.1039/C4TC00505H
- Full Text:
Optical nonlinearities in non-peripherally substituted pyridyloxy phthalocyanines: a combined effect of symmetry, ring-strain and demetallation
- Sanusi, Kayode, Antunes, Edith M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7301 , http://hdl.handle.net/10962/d1020375
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively. , Original publication is available at http://dx.doi.org/10.1039/C3DT52462K , Arbortext Advanced Print Publisher 9.1.520/W Unicode , Acrobat Distiller 10.0.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7301 , http://hdl.handle.net/10962/d1020375
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively. , Original publication is available at http://dx.doi.org/10.1039/C3DT52462K , Arbortext Advanced Print Publisher 9.1.520/W Unicode , Acrobat Distiller 10.0.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
Photocatalytic behavior of phthalocyanine-silver nanoparticle conjugates supported on polystyrene fibers
- Khoza, Phindile, Nyokong, Tebello
- Authors: Khoza, Phindile , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7317 , http://hdl.handle.net/10962/d1020561
- Description: Herein, carbazole derivatized non-peripheral (1,(4)-tetra(carbazol-2-yloxy)phthalocyaninatozinc(II), 3-TCbZnPc) and peripheral (2,(3)-tetra(carbazol-2-yloxy)phthalocyaninato zinc(II), 4-TCbZnPc) are conjugated to silver nanoparticles and their photochemical and photophysical behavior are reported. The presence of silver nanoparticles resulted in reduced fluorescence, and increased triplet and singlet oxygen quantum yields. The conjugates were further electrospun into polystyrene fibers, and employed for the photodegradation of methyl orange. The photodegradation of methyl orange using all functionalized fibers followed first order kinetics, and was faster when the conjugates with silver nanoparticles were used. The non-peripherally substituted 3-TCbZnPc gave better photocatalytic activity compared to its peripherally substituted counterpart (4-TCbZnPc). The hybrid electrospun fibers provide great potential as active photocatalysts for degrading organic pollutants. , Online publication is available at http://dx.doi.org/10.1016/j.molcata.2014.07.031
- Full Text: false
- Authors: Khoza, Phindile , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7317 , http://hdl.handle.net/10962/d1020561
- Description: Herein, carbazole derivatized non-peripheral (1,(4)-tetra(carbazol-2-yloxy)phthalocyaninatozinc(II), 3-TCbZnPc) and peripheral (2,(3)-tetra(carbazol-2-yloxy)phthalocyaninato zinc(II), 4-TCbZnPc) are conjugated to silver nanoparticles and their photochemical and photophysical behavior are reported. The presence of silver nanoparticles resulted in reduced fluorescence, and increased triplet and singlet oxygen quantum yields. The conjugates were further electrospun into polystyrene fibers, and employed for the photodegradation of methyl orange. The photodegradation of methyl orange using all functionalized fibers followed first order kinetics, and was faster when the conjugates with silver nanoparticles were used. The non-peripherally substituted 3-TCbZnPc gave better photocatalytic activity compared to its peripherally substituted counterpart (4-TCbZnPc). The hybrid electrospun fibers provide great potential as active photocatalysts for degrading organic pollutants. , Online publication is available at http://dx.doi.org/10.1016/j.molcata.2014.07.031
- Full Text: false
Photophysichochemical behavior of carbazole derivatized zinc phthalocyanine in the presence of ZnO microparticles and when embedded in electrospun fibers
- Khoza, Phindile, Antunes, Edith M, Nyokong, Tebello
- Authors: Khoza, Phindile , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7303 , http://hdl.handle.net/10962/d1020380
- Description: The synthesis of a zinc phthalocyanine complex tetrasubstituted with carbazole functionality at the peripheral position (complex 4) is reported. The singlet oxygen quantum yield of the complex was found to be 0.83 in dimethylformamide (DMF). The complex was subsequently conjugated to zinc oxide microparticles (ZnOMPs), the conjugation (formation of the amide bond) was confirmed by IR spectroscopy. The presence of ZnOMPs was found to reduce the singlet oxygen produced (ΦΔ = 0.63) in DMF. Polystyrene electrospun fibers of complex 4 alone and its conjugate to ZnOMPs were found to be thermally stable. The singlet oxygen quantum yield of the modified electrospun fibers was determined in aqueous media with ADMA as a singlet oxygen quencher and were 0.25 and 0.20 for complex 4 and 4-ZnOMPs embedded in fibers, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.dyepig.2013.12.019
- Full Text: false
- Authors: Khoza, Phindile , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7303 , http://hdl.handle.net/10962/d1020380
- Description: The synthesis of a zinc phthalocyanine complex tetrasubstituted with carbazole functionality at the peripheral position (complex 4) is reported. The singlet oxygen quantum yield of the complex was found to be 0.83 in dimethylformamide (DMF). The complex was subsequently conjugated to zinc oxide microparticles (ZnOMPs), the conjugation (formation of the amide bond) was confirmed by IR spectroscopy. The presence of ZnOMPs was found to reduce the singlet oxygen produced (ΦΔ = 0.63) in DMF. Polystyrene electrospun fibers of complex 4 alone and its conjugate to ZnOMPs were found to be thermally stable. The singlet oxygen quantum yield of the modified electrospun fibers was determined in aqueous media with ADMA as a singlet oxygen quencher and were 0.25 and 0.20 for complex 4 and 4-ZnOMPs embedded in fibers, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.dyepig.2013.12.019
- Full Text: false
Polyamide nanofiber membranes functionalized with zinc phthalocyanines
- Goethals, Annelies, Mugadza, Tawanda, Arslanoglu, Yasin, Zugle, Ruphino, Antunes, Edith M, Hulle, Stijn W H Van, Nyokong, Tebello, Clerck, Karen De
- Authors: Goethals, Annelies , Mugadza, Tawanda , Arslanoglu, Yasin , Zugle, Ruphino , Antunes, Edith M , Hulle, Stijn W H Van , Nyokong, Tebello , Clerck, Karen De
- Language: English
- Type: Article
- Identifier: vital:7313 , http://hdl.handle.net/10962/d1020539
- Description: Electrospinning is an efficient method for the production of polyamide nanofiber membranes that are suitable for water filtration. Previous studies have shown that nanofiber membranes have high clean water permeability. The pathogen removal efficiency can be improved by functionalization with (organic) biocides. However, these membranes, like other membranes, are vulnerable to fouling which reduces the filtration efficiency. Therefore the present article investigates the potential of zinc phthalocyanines, which can produce singlet oxygen in the presence of visible light, as a functionalizing agent. The polyamide nanofiber membranes were functionalized with phthalocyanines using both a pre-functionalizing and post-functionalizing method. Only the post-functionalization method shows to result in nanofiber membranes capable of producing singlet oxygen. After 30 min 45% of 1,2-diphenylisobenzofuran (DPBF), used as an oxygen quencher, was removed by reaction with singlet oxygen. This resulted in a removal rate of 0.33 mol DBPF mol−1Zn min−1. During short term leaching tests, phthalocyanines could not be detected. , Original publication is available at http://dx.doi.org/10.1002/app.40486
- Full Text: false
- Authors: Goethals, Annelies , Mugadza, Tawanda , Arslanoglu, Yasin , Zugle, Ruphino , Antunes, Edith M , Hulle, Stijn W H Van , Nyokong, Tebello , Clerck, Karen De
- Language: English
- Type: Article
- Identifier: vital:7313 , http://hdl.handle.net/10962/d1020539
- Description: Electrospinning is an efficient method for the production of polyamide nanofiber membranes that are suitable for water filtration. Previous studies have shown that nanofiber membranes have high clean water permeability. The pathogen removal efficiency can be improved by functionalization with (organic) biocides. However, these membranes, like other membranes, are vulnerable to fouling which reduces the filtration efficiency. Therefore the present article investigates the potential of zinc phthalocyanines, which can produce singlet oxygen in the presence of visible light, as a functionalizing agent. The polyamide nanofiber membranes were functionalized with phthalocyanines using both a pre-functionalizing and post-functionalizing method. Only the post-functionalization method shows to result in nanofiber membranes capable of producing singlet oxygen. After 30 min 45% of 1,2-diphenylisobenzofuran (DPBF), used as an oxygen quencher, was removed by reaction with singlet oxygen. This resulted in a removal rate of 0.33 mol DBPF mol−1Zn min−1. During short term leaching tests, phthalocyanines could not be detected. , Original publication is available at http://dx.doi.org/10.1002/app.40486
- Full Text: false
Spectral properties and photophysical behaviour of water soluble cationic Mg(II) and Al(III) phthalocyanines
- Idowu, Mopelola A, Arslanoglu, Yasin, Nyokong, Tebello
- Authors: Idowu, Mopelola A , Arslanoglu, Yasin , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7277 , http://hdl.handle.net/10962/d1020292
- Description: Peripherally and non-peripherally tetrasubstituted-[(N-methyl-2-pyridylthio)]phthalocyaninato magnesium (II) (5 and 6) and chloro aluminium (III) (7 and 8) tetraiodide have been synthesized and characterized. The photophysical properties of the complexes in dimethyl sulfoxide (DMSO) and aqueous medium in the presence and absence of cremophore EL have been studied. These complexes show high solubility in aqueous medium though they were aggregated. The triplet state quantum yields (FT) and the triplet lifetimes (tT) were found to be higher in DMSO with ΦT ranging from 0.32 to 0.51, while tT ranged from 282 to 622 ms in DMSO, compared to aqueous medium (pH 7.4 buffer) where ΦT ranged from 0.15 to 0.19 and tT from 26 to 35 ms. Addition of cremophore EL in aqueous solution resulted in partial disaggregation and increased photoactivity. The fluorescence lifetimes of the complexes showed strong dependence on their immediate environment. The ionic magnesium(II) and aluminium(III) phthalocyanines strongly bind to bovine serum albumin (BSA). , Original publication is available at http://dx.doi.org/10.2478/s11532-013-0388-z
- Full Text: false
- Authors: Idowu, Mopelola A , Arslanoglu, Yasin , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7277 , http://hdl.handle.net/10962/d1020292
- Description: Peripherally and non-peripherally tetrasubstituted-[(N-methyl-2-pyridylthio)]phthalocyaninato magnesium (II) (5 and 6) and chloro aluminium (III) (7 and 8) tetraiodide have been synthesized and characterized. The photophysical properties of the complexes in dimethyl sulfoxide (DMSO) and aqueous medium in the presence and absence of cremophore EL have been studied. These complexes show high solubility in aqueous medium though they were aggregated. The triplet state quantum yields (FT) and the triplet lifetimes (tT) were found to be higher in DMSO with ΦT ranging from 0.32 to 0.51, while tT ranged from 282 to 622 ms in DMSO, compared to aqueous medium (pH 7.4 buffer) where ΦT ranged from 0.15 to 0.19 and tT from 26 to 35 ms. Addition of cremophore EL in aqueous solution resulted in partial disaggregation and increased photoactivity. The fluorescence lifetimes of the complexes showed strong dependence on their immediate environment. The ionic magnesium(II) and aluminium(III) phthalocyanines strongly bind to bovine serum albumin (BSA). , Original publication is available at http://dx.doi.org/10.2478/s11532-013-0388-z
- Full Text: false
Synthesis and characterization of quantum dots designed for biomedical use
- Kuzyniak, Weronika, Adegoke, Oluwasesan, Sekhosana, Kutloano, D’Souza, Sarah, Tshangana, Sesethu Charmaine, Hoffmann, Björn, Ermilov, Eugeny A., Nyokong, Tebello, Höpfner, Michael
- Authors: Kuzyniak, Weronika , Adegoke, Oluwasesan , Sekhosana, Kutloano , D’Souza, Sarah , Tshangana, Sesethu Charmaine , Hoffmann, Björn , Ermilov, Eugeny A. , Nyokong, Tebello , Höpfner, Michael
- Language: English
- Type: Article
- Identifier: vital:7310 , http://hdl.handle.net/10962/d1020387
- Description: Semiconductor quantum dots (QDs) have become promising nanoparticles for a wide variety of biomedical applications. However, the major drawback of QDs is their potential toxicity. Here, we determined possible cytotoxic effects of a set of QDs by systematic photophysical evaluation in vitro as well as in vivo. QDs were synthesized by the hydrothermal aqueous route with sizes in the range of 2.0–3.5 nm. Cytotoxic effects of QDs were studied in the human pancreatic carcinoid cell line BON. Cadmium telluride QDs with or without zinc sulfide shell and coated with 3-mercaptopropionic acid (MPA) were highly cytotoxic even at nanomolar concentrations. Capping with l-glutathione (GSH) or thioglycolic acid (TGA) reduced the cytotoxicity of cadmium telluride QDs and cadmium selenide QDs. Determination of the toxicity of QDs revealed IC50 values in the micromolar range. In vivo studies showed good tolerability of CdSe QDs with ZnS shell and GSH capping. We could demonstrate that QDs with ZnS shell and GSH capping exhibit low toxicity and good tolerability in cell models and living organisms. These QDs appear to be promising candidates for biomedical applications such as drug delivery for enhanced chemotherapy or targeted delivery of light sensitive substances for photodynamic therapy. , Original publication is available at http://dx.doi.org/10.1016/j.ijpharm.2014.03.037
- Full Text: false
- Authors: Kuzyniak, Weronika , Adegoke, Oluwasesan , Sekhosana, Kutloano , D’Souza, Sarah , Tshangana, Sesethu Charmaine , Hoffmann, Björn , Ermilov, Eugeny A. , Nyokong, Tebello , Höpfner, Michael
- Language: English
- Type: Article
- Identifier: vital:7310 , http://hdl.handle.net/10962/d1020387
- Description: Semiconductor quantum dots (QDs) have become promising nanoparticles for a wide variety of biomedical applications. However, the major drawback of QDs is their potential toxicity. Here, we determined possible cytotoxic effects of a set of QDs by systematic photophysical evaluation in vitro as well as in vivo. QDs were synthesized by the hydrothermal aqueous route with sizes in the range of 2.0–3.5 nm. Cytotoxic effects of QDs were studied in the human pancreatic carcinoid cell line BON. Cadmium telluride QDs with or without zinc sulfide shell and coated with 3-mercaptopropionic acid (MPA) were highly cytotoxic even at nanomolar concentrations. Capping with l-glutathione (GSH) or thioglycolic acid (TGA) reduced the cytotoxicity of cadmium telluride QDs and cadmium selenide QDs. Determination of the toxicity of QDs revealed IC50 values in the micromolar range. In vivo studies showed good tolerability of CdSe QDs with ZnS shell and GSH capping. We could demonstrate that QDs with ZnS shell and GSH capping exhibit low toxicity and good tolerability in cell models and living organisms. These QDs appear to be promising candidates for biomedical applications such as drug delivery for enhanced chemotherapy or targeted delivery of light sensitive substances for photodynamic therapy. , Original publication is available at http://dx.doi.org/10.1016/j.ijpharm.2014.03.037
- Full Text: false
Unsymmetrically Substituted Nickel Triazatetra-Benzcorrole and Phthalocynanine Complexes: Conjugation to Quantum Dots and Applications as Fluorescent “Turn ON” Sensors
- Adegoke, Oluwasesan, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7311 , http://hdl.handle.net/10962/d1020403
- Description: We report on the design and application of fluorescent nanoprobes based on the covalent linking of L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg2+ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg2+ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg2+ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs. , Original publication is available at http://dx.doi.org/10.1007/s10895-013-1317-4
- Full Text: false
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7311 , http://hdl.handle.net/10962/d1020403
- Description: We report on the design and application of fluorescent nanoprobes based on the covalent linking of L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg2+ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg2+ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg2+ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs. , Original publication is available at http://dx.doi.org/10.1007/s10895-013-1317-4
- Full Text: false