Enhanced optical limiting behaviour of indium phthalocyanine derivatives when in solution or embedded in poly (acrylic acid) or poly (methyl methacrylate) polymers
- Sanusi, Kayode, Nyokong, Tebello
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189445 , vital:44847 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.02.003"
- Description: The optical limiting performance of indium phthalocyanine-based polymer thin-films with large nonlinear absorption coefficients (βeff) and low limiting threshold intensity (Ilim) are described. The absorption cross-sections and the population dynamics of the excited states are also reported. The excited state absorption cross-sections (σexc) are shown to depend on the transition moment between the T1 and T2 states. βeff values have been shown to be related to the population density of the molecules in the T1 state. The improved optical limiting performance recorded for the investigated phthalocyanine complexes in the presence of polymer matrices has been attributed to the aggregation effects of the complexes in the polymer thin-films. The optical properties of the indium phthalocyanine moieties were found to possess robust sensitivity to a change of the polymer materials.
- Full Text:
- Date Issued: 2015
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189445 , vital:44847 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.02.003"
- Description: The optical limiting performance of indium phthalocyanine-based polymer thin-films with large nonlinear absorption coefficients (βeff) and low limiting threshold intensity (Ilim) are described. The absorption cross-sections and the population dynamics of the excited states are also reported. The excited state absorption cross-sections (σexc) are shown to depend on the transition moment between the T1 and T2 states. βeff values have been shown to be related to the population density of the molecules in the T1 state. The improved optical limiting performance recorded for the investigated phthalocyanine complexes in the presence of polymer matrices has been attributed to the aggregation effects of the complexes in the polymer thin-films. The optical properties of the indium phthalocyanine moieties were found to possess robust sensitivity to a change of the polymer materials.
- Full Text:
- Date Issued: 2015
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
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- 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.
- Full Text:
- Date Issued: 2015
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- 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.
- Full Text:
- Date Issued: 2015
Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines
- D'Souza, Sarah, Moeno, Sharon, Nyokong, Tebello
- Authors: D'Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189741 , vital:44927 , xlink:href="https://doi.org/10.1016/j.poly.2014.09.012"
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis- (mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods.
- Full Text:
- Date Issued: 2015
- Authors: D'Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189741 , vital:44927 , xlink:href="https://doi.org/10.1016/j.poly.2014.09.012"
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis- (mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods.
- Full Text:
- Date Issued: 2015
Comparative electrocatalytic studies of nanocomposites of mixed and covalently linked multiwalled carbon nanotubes and 4-(4, 6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt (II)
- Nyoni, Stephen, Nyokong, Tebello
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189285 , vital:44834 , xlink:href="https://doi.org/10.1016/j.poly.2015.05.038"
- Description: Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards L-cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite.
- Full Text:
- Date Issued: 2015
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189285 , vital:44834 , xlink:href="https://doi.org/10.1016/j.poly.2015.05.038"
- Description: Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards L-cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite.
- Full Text:
- Date Issued: 2015
Photodynamic antimicrobial chemotherapy activity of gallium tetra-(4-carboxyphenyl) porphyrin when conjugated to differently shaped platinum nanoparticles
- Managa, Muthumuni, Nyokong, Tebello
- Authors: Managa, Muthumuni , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7297 , http://hdl.handle.net/10962/d1020360
- Description: This work reports on the conjugation of differently shaped Pt nanoparticles (PtNPs) with ClGa(III) 5,10,15,20-tetrakis-(4-carboxyphenyl) porphyrin (ClGaTCPP). The resulting conjugates were used for photodynamic antimicrobial chemotherapy against Staphylococcus aureus. The degree of photo-inactivation is dependent on concentration of the conjugates, light dose (fluence) and illumination time. The log reduction obtained for ClGaTCPP when conjugated to cubic PtNPs was 4.64 log (which indicate 99.99% of the bacteria have been killed), which is much higher than 3.94 log unit for ClGaTCPP-Hexagonal PtNPs and 3.31 log units for ClGaTCPP-Unshaped PtNPs. ClGaTCPP alone gave a log unit reduction of less than 3, showing the importance of conjugation to PtNPs. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.06.077
- Full Text: false
- Authors: Managa, Muthumuni , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7297 , http://hdl.handle.net/10962/d1020360
- Description: This work reports on the conjugation of differently shaped Pt nanoparticles (PtNPs) with ClGa(III) 5,10,15,20-tetrakis-(4-carboxyphenyl) porphyrin (ClGaTCPP). The resulting conjugates were used for photodynamic antimicrobial chemotherapy against Staphylococcus aureus. The degree of photo-inactivation is dependent on concentration of the conjugates, light dose (fluence) and illumination time. The log reduction obtained for ClGaTCPP when conjugated to cubic PtNPs was 4.64 log (which indicate 99.99% of the bacteria have been killed), which is much higher than 3.94 log unit for ClGaTCPP-Hexagonal PtNPs and 3.31 log units for ClGaTCPP-Unshaped PtNPs. ClGaTCPP alone gave a log unit reduction of less than 3, showing the importance of conjugation to PtNPs. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.06.077
- Full Text: false
Fluorescence behavior and singlet oxygen generating abilities of aluminum phthalocyanine in the presence of anisotropic gold nanoparticles
- Mthethwa, Thandekile, Nyokong, Tebello
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193598 , vital:45351 , xlink:href="https://doi.org/10.1016/j.jlumin.2014.09.005"
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs.
- Full Text:
- Date Issued: 2015
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193598 , vital:45351 , xlink:href="https://doi.org/10.1016/j.jlumin.2014.09.005"
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs.
- Full Text:
- Date Issued: 2015
Photodynamic therapy effect of zinc monoamino phthalocyanine–folic acid conjugate adsorbed on single walled carbon nanotubes on melanoma cells
- Ogbodu, Racheal O, Ndhundhuma, Ivy, Karstten, Aletta, Nyokong, Tebello
- Authors: Ogbodu, Racheal O , Ndhundhuma, Ivy , Karstten, Aletta , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241400 , vital:50936 , xlink:href="https://doi.org/10.1016/j.saa.2014.09.033"
- Description: This work reports on the photodynamic therapy effect of zinc monoamino phthalocyanine linked to folic acid represented as ZnMAPc-FA, which was further immobilized onto single walled carbon nanotube represented as ZnMAPc-FA-SWCNT on melanoma A375 cell line, the effect of SWCNT-FA (without ZnMAPc) was also examined. All the compounds were non-toxic to the melanoma A375 cell line in the absence of light. Upon irradiation of the melanoma A375 cell line with a 676 nm diode laser at a power density of 98 mW/cm2 at 5 J/cm2 about 60% and 63% cell death was observed in the presence of ZnMAPc-FA and ZnMAPc-FA-SWCNT respectively. SWCNT-FA had no significant photodynamic therapy or photothermal effect to the cell, only 23% of cell death was observed after irradiation.
- Full Text:
- Date Issued: 2015
- Authors: Ogbodu, Racheal O , Ndhundhuma, Ivy , Karstten, Aletta , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241400 , vital:50936 , xlink:href="https://doi.org/10.1016/j.saa.2014.09.033"
- Description: This work reports on the photodynamic therapy effect of zinc monoamino phthalocyanine linked to folic acid represented as ZnMAPc-FA, which was further immobilized onto single walled carbon nanotube represented as ZnMAPc-FA-SWCNT on melanoma A375 cell line, the effect of SWCNT-FA (without ZnMAPc) was also examined. All the compounds were non-toxic to the melanoma A375 cell line in the absence of light. Upon irradiation of the melanoma A375 cell line with a 676 nm diode laser at a power density of 98 mW/cm2 at 5 J/cm2 about 60% and 63% cell death was observed in the presence of ZnMAPc-FA and ZnMAPc-FA-SWCNT respectively. SWCNT-FA had no significant photodynamic therapy or photothermal effect to the cell, only 23% of cell death was observed after irradiation.
- Full Text:
- Date Issued: 2015
Nonlinear optical response of tetra and mono substituted zinc phthalocyanine complexes
- Fashina, Adedayo, Nyokong, Tebello
- Authors: Fashina, Adedayo , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7281 , http://hdl.handle.net/10962/d1020318 , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2015.06.003
- Description: The nonlinear absorption properties of 6 mono-substituted and 3 symmetric zinc phthalocyanine complexes have been studied in dimethylsulfoxide (DMSO) using 10 ns pulses at 532 nm. The non linear absorption of the complexes has been studied using the Z-scan technique. The study showed that both the singlet and triplet excited states contribute to the non linear absorption behavior. The nonlinear third-order susceptibility and second-order hyperpolarizability values of the complexes are reported. It was observed that two of the symmetric phthalocyanine complexes (5-α substituted with aminophenoxy and 9-β substituted with carboxyphenoxy) showed better and promising optical nonlinearity when compared to the other complexes studied.
- Full Text: false
- Date Issued: 2015
- Authors: Fashina, Adedayo , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7281 , http://hdl.handle.net/10962/d1020318 , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2015.06.003
- Description: The nonlinear absorption properties of 6 mono-substituted and 3 symmetric zinc phthalocyanine complexes have been studied in dimethylsulfoxide (DMSO) using 10 ns pulses at 532 nm. The non linear absorption of the complexes has been studied using the Z-scan technique. The study showed that both the singlet and triplet excited states contribute to the non linear absorption behavior. The nonlinear third-order susceptibility and second-order hyperpolarizability values of the complexes are reported. It was observed that two of the symmetric phthalocyanine complexes (5-α substituted with aminophenoxy and 9-β substituted with carboxyphenoxy) showed better and promising optical nonlinearity when compared to the other complexes studied.
- Full Text: false
- Date Issued: 2015
Improved triplet state parameters for indium octacarboxy phthalocyanines when conjugated to quantum dots and magnetite nanoparticles
- Tshangana, Charmaine, Nyokong, Tebello
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7252 , http://hdl.handle.net/10962/d1020260
- Description: Fe3O4 magnetic nanoparticles (MNPs) and glutathione (GSH) capped CdSe@ZnS quantum dots (QDs) were separately coordinated to indium octacarboxy phthalocyanine (InPc(COOH)8) to form ClInPc(COOH)8–MNPs and ClInPc(COOH)8–GSH–CdSe@ZnS, respectively. The photophysical parameters (triplet state and fluorescence quantum yields and lifetimes) were determined for the conjugates. The triplet quantum yields increased from ΦT = 0.49 for InPc(COOH)8 alone to ΦT = 0.61 and 0.56 for InPc(COOH)8 in the conjugates: ClInPc(COOH)8–MNPs and ClInPc(COOH)8–GSH–CdSe@ZnS, respectively. The lifetimes also became longer for the conjugates compared to Pc alone. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.02.040
- Full Text: false
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7252 , http://hdl.handle.net/10962/d1020260
- Description: Fe3O4 magnetic nanoparticles (MNPs) and glutathione (GSH) capped CdSe@ZnS quantum dots (QDs) were separately coordinated to indium octacarboxy phthalocyanine (InPc(COOH)8) to form ClInPc(COOH)8–MNPs and ClInPc(COOH)8–GSH–CdSe@ZnS, respectively. The photophysical parameters (triplet state and fluorescence quantum yields and lifetimes) were determined for the conjugates. The triplet quantum yields increased from ΦT = 0.49 for InPc(COOH)8 alone to ΦT = 0.61 and 0.56 for InPc(COOH)8 in the conjugates: ClInPc(COOH)8–MNPs and ClInPc(COOH)8–GSH–CdSe@ZnS, respectively. The lifetimes also became longer for the conjugates compared to Pc alone. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.02.040
- Full Text: false
Surface modification of silica-coated gadolinium oxide nanoparticles with zinc tetracarboxyphenoxy phthalocyanine for the photodegradation of Orange G
- Ledwaba, Mpho, Masilela, Nkosiphile, Nyokong, Tebello, Antunes, Edith M
- Authors: Ledwaba, Mpho , Masilela, Nkosiphile , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193621 , vital:45353 , xlink:href="https://doi.org/10.1016/j.molcata.2015.03.023"
- Description: Zinc tetracarboxyphenoxy phthalocyanine was covalently linked to Gd2O3 nanoparticles for the photocatalytic degradation of Orange G. Characterization of the composite was carried out using XRD, TEM, XPS, UV–vis spectroscopy and FT-IR spectroscopy. The composite showed improved photophysical properties over the phthalocyanine alone and the catalyst was found to be reusable. Analyses of the photodegradation rates of the azo dye indicated pseudo first-order kinetics.
- Full Text:
- Date Issued: 2015
- Authors: Ledwaba, Mpho , Masilela, Nkosiphile , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193621 , vital:45353 , xlink:href="https://doi.org/10.1016/j.molcata.2015.03.023"
- Description: Zinc tetracarboxyphenoxy phthalocyanine was covalently linked to Gd2O3 nanoparticles for the photocatalytic degradation of Orange G. Characterization of the composite was carried out using XRD, TEM, XPS, UV–vis spectroscopy and FT-IR spectroscopy. The composite showed improved photophysical properties over the phthalocyanine alone and the catalyst was found to be reusable. Analyses of the photodegradation rates of the azo dye indicated pseudo first-order kinetics.
- Full Text:
- Date Issued: 2015
Structural and optical properties of alloyed quaternary CdSeTeS core and CdSeTeS/ZnS core–shell quantum dots
- Adegoke, Oluwasesan, Nyokong, Tebello, Forbes, Patricia B C
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193575 , vital:45349 , xlink:href="https://doi.org/10.1016/j.jallcom.2015.05.083"
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface.
- Full Text:
- Date Issued: 2015
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193575 , vital:45349 , xlink:href="https://doi.org/10.1016/j.jallcom.2015.05.083"
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface.
- Full Text:
- Date Issued: 2015
Fluorescence behavior and singlet oxygen generating abilities of aluminum phthalocyanine in the presence of anisotropic gold nanoparticles
- Mthethwa, Thandekile, Nyokong, Tebello
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189865 , vital:44941 , xlink:href="https://doi.org/10.1016/j.jlumin.2014.09.005"
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs.
- Full Text:
- Date Issued: 2015
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189865 , vital:44941 , xlink:href="https://doi.org/10.1016/j.jlumin.2014.09.005"
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs.
- Full Text:
- Date Issued: 2015
Trypanosoma brucei J protein 2 is a stress inducible and essential Hsp40
- Ludewig, Michael H, Boshoff, Aileen, Horn, David, Blatch, Gregory L
- Authors: Ludewig, Michael H , Boshoff, Aileen , Horn, David , Blatch, Gregory L
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431798 , vital:72804 , xlink:href="https://doi.org/10.1016/j.biocel.2014.12.016"
- Description: Hsp40 proteins (also known as DnaJ or J proteins) serve as co-chaperones for Hsp70, but also display evidence of independent chaperone function. Furthermore, certain Hsp40s have been shown to be stress-inducible and essential. Trypanosomatids display a remarkable diversification of Hsp40 proteins, with numerous distinct Hsp40-like proteins encoded in the Trypanosoma brucei genome. This study investigated the role of one of the six T. brucei Type I Hsp40s, T. brucei J protein 2 (Tbj2). We found that Tbj2 was heat stress-inducible, and that knockdown using RNA interference resulted in a severe growth defect under normal growth temperatures. Furthermore, a green fluorescent protein (GFP)-Tbj2 fusion protein was found to be localized to the cytosol of T. brucei. Taken together, these data suggest that Tbj2 is not functionally equivalent to the other five Type I Hsp40s, and that it is an essential, cytosolic, and stress-inducible chaperone, potentially playing an important role in protein biogenesis in T. brucei.
- Full Text:
- Date Issued: 2015
- Authors: Ludewig, Michael H , Boshoff, Aileen , Horn, David , Blatch, Gregory L
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431798 , vital:72804 , xlink:href="https://doi.org/10.1016/j.biocel.2014.12.016"
- Description: Hsp40 proteins (also known as DnaJ or J proteins) serve as co-chaperones for Hsp70, but also display evidence of independent chaperone function. Furthermore, certain Hsp40s have been shown to be stress-inducible and essential. Trypanosomatids display a remarkable diversification of Hsp40 proteins, with numerous distinct Hsp40-like proteins encoded in the Trypanosoma brucei genome. This study investigated the role of one of the six T. brucei Type I Hsp40s, T. brucei J protein 2 (Tbj2). We found that Tbj2 was heat stress-inducible, and that knockdown using RNA interference resulted in a severe growth defect under normal growth temperatures. Furthermore, a green fluorescent protein (GFP)-Tbj2 fusion protein was found to be localized to the cytosol of T. brucei. Taken together, these data suggest that Tbj2 is not functionally equivalent to the other five Type I Hsp40s, and that it is an essential, cytosolic, and stress-inducible chaperone, potentially playing an important role in protein biogenesis in T. brucei.
- Full Text:
- Date Issued: 2015
PFB0595w is a Plasmodium falciparum J protein that co-localizes with PfHsp70-1 and can stimulate its in vitro ATP hydrolysis activity
- Njunge, James M, Mandal, Pradipta, Przyborski, Jude M, Boshoff, Aileen, Pesce, Eva-Rachele, Blatch, Gregory L
- Authors: Njunge, James M , Mandal, Pradipta , Przyborski, Jude M , Boshoff, Aileen , Pesce, Eva-Rachele , Blatch, Gregory L
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431739 , vital:72800 , xlink:href="https://doi.org/10.1016/j.biocel.2015.02.008"
- Description: Heat shock proteins, many of which function as molecular chaperones, play important roles in the lifecycle and pathogenesis of the malaria parasite, Plasmodium falciparum. The P. falciparum heat shock protein 70 (PfHsp70) family of chaperones is potentially regulated by a large complement of J proteins that localize to various intracellular compartments including the infected erythrocyte cytosol. While PfHsp70-1 has been shown to be an abundant cytosolic chaperone, its regulation by J proteins is poorly understood. In this study, we characterized the J protein PFB0595w, a homologue of the well-studied yeast cytosolic J protein, Sis1. PFB0595w, similarly to PfHsp70-1, was localized to the parasite cytosol and its expression was upregulated by heat shock. Additionally, recombinant PFB0595w was shown to be dimeric and to stimulate the in vitro ATPase activity of PfHsp70-1. Overall, the expression, localization and biochemical data for PFB0595w suggest that it may function as a cochaperone of PfHsp70-1, and advances current knowledge on the chaperone machinery of the parasite.
- Full Text:
- Date Issued: 2015
- Authors: Njunge, James M , Mandal, Pradipta , Przyborski, Jude M , Boshoff, Aileen , Pesce, Eva-Rachele , Blatch, Gregory L
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431739 , vital:72800 , xlink:href="https://doi.org/10.1016/j.biocel.2015.02.008"
- Description: Heat shock proteins, many of which function as molecular chaperones, play important roles in the lifecycle and pathogenesis of the malaria parasite, Plasmodium falciparum. The P. falciparum heat shock protein 70 (PfHsp70) family of chaperones is potentially regulated by a large complement of J proteins that localize to various intracellular compartments including the infected erythrocyte cytosol. While PfHsp70-1 has been shown to be an abundant cytosolic chaperone, its regulation by J proteins is poorly understood. In this study, we characterized the J protein PFB0595w, a homologue of the well-studied yeast cytosolic J protein, Sis1. PFB0595w, similarly to PfHsp70-1, was localized to the parasite cytosol and its expression was upregulated by heat shock. Additionally, recombinant PFB0595w was shown to be dimeric and to stimulate the in vitro ATPase activity of PfHsp70-1. Overall, the expression, localization and biochemical data for PFB0595w suggest that it may function as a cochaperone of PfHsp70-1, and advances current knowledge on the chaperone machinery of the parasite.
- Full Text:
- Date Issued: 2015
Optimisation of an electrochemical impedance spectroscopy aptasensor by exploiting quartz crystal microbalance with dissipation signals
- Formisanoa, Nello, Jolly, Pawan, Bhalla, Nikhil, Cromhout, Mary, Flanagan, Shane P, Fogel, Ronen, Limson, Janice L, Estrela, Pedro
- Authors: Formisanoa, Nello , Jolly, Pawan , Bhalla, Nikhil , Cromhout, Mary , Flanagan, Shane P , Fogel, Ronen , Limson, Janice L , Estrela, Pedro
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431699 , vital:72797 , xlink:href="https://doi.org/10.1016/j.snb.2015.05.049"
- Description: The response of an Electrochemical Impedance Spectroscopy (EIS) sensor using DNA aptamers is affected by many factors, such as DNA density, charge and conformational changes upon DNA-target binding, and buffer conditions. We report here for the first time on the optimisation of an EIS aptamer-based sensor by using Quartz Crystal Microbalance with Dissipation mode (QCM-D). As a case study, we employed a DNA aptamer against Prostate-Specific Antigen (PSA). PSA detection was achieved by functionalising the gold sensor surface via thiol chemistry with different ratios of thiolated-DNA aptamer and 6-mercapto-1-hexanol (MCH) used as spacer molecules. PSA binding efficiency can be monitored by measuring QCM-D signals which not only provide information about the mass of PSA bound on the sensor surface, but also crucial information about the aptamer conformation and layer hydration.
- Full Text:
- Date Issued: 2015
- Authors: Formisanoa, Nello , Jolly, Pawan , Bhalla, Nikhil , Cromhout, Mary , Flanagan, Shane P , Fogel, Ronen , Limson, Janice L , Estrela, Pedro
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431699 , vital:72797 , xlink:href="https://doi.org/10.1016/j.snb.2015.05.049"
- Description: The response of an Electrochemical Impedance Spectroscopy (EIS) sensor using DNA aptamers is affected by many factors, such as DNA density, charge and conformational changes upon DNA-target binding, and buffer conditions. We report here for the first time on the optimisation of an EIS aptamer-based sensor by using Quartz Crystal Microbalance with Dissipation mode (QCM-D). As a case study, we employed a DNA aptamer against Prostate-Specific Antigen (PSA). PSA detection was achieved by functionalising the gold sensor surface via thiol chemistry with different ratios of thiolated-DNA aptamer and 6-mercapto-1-hexanol (MCH) used as spacer molecules. PSA binding efficiency can be monitored by measuring QCM-D signals which not only provide information about the mass of PSA bound on the sensor surface, but also crucial information about the aptamer conformation and layer hydration.
- Full Text:
- Date Issued: 2015
Transformative, transgressive social learning: Rethinking higher education pedagogy in times of systemic global dysfunction
- Lotz-Sisitka, Heila, Wals, Arjen E J, Kronlid, David O, McGarry, Dylan K
- Authors: Lotz-Sisitka, Heila , Wals, Arjen E J , Kronlid, David O , McGarry, Dylan K
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/372794 , vital:66623 , xlink:href="https://doi.org/10.1016/j.cosust.2015.07.018"
- Description: The nature of the sustainability challenges currently at hand is such that dominant pedagogies and forms of learning that characterize higher education need to be reconsidered to enable students and staff to deal with accelerating change, increasing complexity, contested knowledge claims and inevitable uncertainty. In this contribution we identified four streams of emerging transformative, transgressive learning research and praxis in the sustainability sciences that appear generative of a higher education pedagogy that appears more responsive to the key challenges of our time: (1) reflexive social learning and capabilities theory, (2) critical phenomenology, (3) socio-cultural and cultural historical activity theory, and (4) new social movement, postcolonial and decolonisation theory. The paper critiques the current tendency in sustainability science and learning to rely on resilience and adaptive capacity building and argues that in order to break with maladaptive resilience of unsustainable systems it is essential to strengthen transgressive learning and disruptive capacity-building.
- Full Text:
- Date Issued: 2015
- Authors: Lotz-Sisitka, Heila , Wals, Arjen E J , Kronlid, David O , McGarry, Dylan K
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/372794 , vital:66623 , xlink:href="https://doi.org/10.1016/j.cosust.2015.07.018"
- Description: The nature of the sustainability challenges currently at hand is such that dominant pedagogies and forms of learning that characterize higher education need to be reconsidered to enable students and staff to deal with accelerating change, increasing complexity, contested knowledge claims and inevitable uncertainty. In this contribution we identified four streams of emerging transformative, transgressive learning research and praxis in the sustainability sciences that appear generative of a higher education pedagogy that appears more responsive to the key challenges of our time: (1) reflexive social learning and capabilities theory, (2) critical phenomenology, (3) socio-cultural and cultural historical activity theory, and (4) new social movement, postcolonial and decolonisation theory. The paper critiques the current tendency in sustainability science and learning to rely on resilience and adaptive capacity building and argues that in order to break with maladaptive resilience of unsustainable systems it is essential to strengthen transgressive learning and disruptive capacity-building.
- Full Text:
- Date Issued: 2015
The prevalence of planning and management frameworks for trees and green spaces in urban areas of South Africa
- Chishaleshale, M, Shackleton, Charlie M, Gambiza, James, Gumbo, Davison
- Authors: Chishaleshale, M , Shackleton, Charlie M , Gambiza, James , Gumbo, Davison
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180884 , vital:43659 , xlink:href="https://doi.org/10.1016/j.ufug.2015.09.012"
- Description: Optimisation of the benefits from urban forestry and greening to urban dwellers and the environment rests on proactive and appropriate management planning, implementation and resourcing. Yet, lessons from the developed world show marked variability in development and adoption of urban tree and green space (UTGS) strategic plans and systematic monitoring and maintenance. Although financial and human resources for UTGS may be constrained in developing world contexts, there is no knowledge of the extent to which local authorities engage in appropriate and timely planning, management and monitoring. Here we examine the UTGS resourcing, planning, maintenance and integration across 28 local municipalities in the two poorest provinces in South Africa. It was revealed that most local municipalities were not managing their UTGS in a planned or systematic manner due to constraining factors such as insufficient funds, insufficient personnel, lack of equipment and lack of political support. Only 7% of the surveyed municipalities had an urban tree management plan and an estimate of the urban tree stock; 32% had tree policies; 21% had tree planting schedules; 11% had tree maintenance schedules. Over 65% claimed to engage other stakeholders in tree planting, but much was passive receipt of trees for planting rather than citizen engagement around species, places and values. Generally, the prevalence of most planning and maintenance elements increased with increasing size of the municipality and the presence of personnel specifically for UTGS management. It is likely that the prevalence of planning and maintenance functions will increase with greater political support from municipal councillors which may also decrease funding challenges.
- Full Text:
- Date Issued: 2015
- Authors: Chishaleshale, M , Shackleton, Charlie M , Gambiza, James , Gumbo, Davison
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180884 , vital:43659 , xlink:href="https://doi.org/10.1016/j.ufug.2015.09.012"
- Description: Optimisation of the benefits from urban forestry and greening to urban dwellers and the environment rests on proactive and appropriate management planning, implementation and resourcing. Yet, lessons from the developed world show marked variability in development and adoption of urban tree and green space (UTGS) strategic plans and systematic monitoring and maintenance. Although financial and human resources for UTGS may be constrained in developing world contexts, there is no knowledge of the extent to which local authorities engage in appropriate and timely planning, management and monitoring. Here we examine the UTGS resourcing, planning, maintenance and integration across 28 local municipalities in the two poorest provinces in South Africa. It was revealed that most local municipalities were not managing their UTGS in a planned or systematic manner due to constraining factors such as insufficient funds, insufficient personnel, lack of equipment and lack of political support. Only 7% of the surveyed municipalities had an urban tree management plan and an estimate of the urban tree stock; 32% had tree policies; 21% had tree planting schedules; 11% had tree maintenance schedules. Over 65% claimed to engage other stakeholders in tree planting, but much was passive receipt of trees for planting rather than citizen engagement around species, places and values. Generally, the prevalence of most planning and maintenance elements increased with increasing size of the municipality and the presence of personnel specifically for UTGS management. It is likely that the prevalence of planning and maintenance functions will increase with greater political support from municipal councillors which may also decrease funding challenges.
- Full Text:
- Date Issued: 2015
Photophysical and non-linear optical behavior of novel tetra alkynyl terminated indium phthalocyanines: Effects of the carbon chain length
- Bankole, Owolabi M, Britton, Jonathan, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7262 , http://hdl.handle.net/10962/d1020271
- Description: We report on the synthesis, photophysical and nonlinear optical behavior of tetra-substituted alkynyl indium phthalocyanine complexes (3a and 3b). Both complexes showed large triplet quantum yields. Nonlinear optical properties were also evaluated for the two complexes at a wavelength of 532 nm using nanosecond Z-scan technique in dimethylsulfoxide. We observed two-photon absorption (2PA) and strong reverse saturable absorption (RSA) as the dominant mechanisms at nanosecond laser excitation. The underlining 2PA and observed RSA were subjected to further scrutiny by comparing the analytical absorption model to the transmittance optical absorption theory. The theoretical results were in good agreement to the observed RSA and the 2PA mechanism. Large two-photon absorption cross-section (1.29 × 10−42 and 1.15 × 10−42 cm4 s/photon), third-order susceptibility (2.10 × 10−14 and 2.15 × 10−14 esu) and hyperpolarizability (2.70 × 10−32 and 3.19 × 10−32 esu) were estimated for complex 3a and 3b, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.12.020
- Full Text: false
- Authors: Bankole, Owolabi M , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7262 , http://hdl.handle.net/10962/d1020271
- Description: We report on the synthesis, photophysical and nonlinear optical behavior of tetra-substituted alkynyl indium phthalocyanine complexes (3a and 3b). Both complexes showed large triplet quantum yields. Nonlinear optical properties were also evaluated for the two complexes at a wavelength of 532 nm using nanosecond Z-scan technique in dimethylsulfoxide. We observed two-photon absorption (2PA) and strong reverse saturable absorption (RSA) as the dominant mechanisms at nanosecond laser excitation. The underlining 2PA and observed RSA were subjected to further scrutiny by comparing the analytical absorption model to the transmittance optical absorption theory. The theoretical results were in good agreement to the observed RSA and the 2PA mechanism. Large two-photon absorption cross-section (1.29 × 10−42 and 1.15 × 10−42 cm4 s/photon), third-order susceptibility (2.10 × 10−14 and 2.15 × 10−14 esu) and hyperpolarizability (2.70 × 10−32 and 3.19 × 10−32 esu) were estimated for complex 3a and 3b, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.12.020
- Full Text: false
A colorimetric probe for dopamine based on gold nanoparticles-electrospun nanofibre composite
- Ngomane, Nokuthula, Torto, Nelson, Krause, Rui W M, Vilakazi, Sibulelo
- Authors: Ngomane, Nokuthula , Torto, Nelson , Krause, Rui W M , Vilakazi, Sibulelo
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195407 , vital:45562 , xlink:href="https://doi.org/10.1016/j.matpr.2015.08.036"
- Description: An easily prepared solid state colorimetric probe for detecting the neurotransmitter dopamine (DA) was developed. The probe, in the form of an electrospun Nylon−6 (N6) nanofibre with embedded un−functionalized gold nanoparticles (UF−AuNPs) produces a clear colour change in the presence of a DA that is detectable by the naked eye. Characterisation of the nanofibre using UV/vis spectroscopy and electron microscopy (TEM) confirmed the formation of the AuNPs in the polymer solution, and that the AuNPs were completely encapsulated within the composite nanofibres before exposure to the analytes. The probe exhibited very high sensitivity towards DA resulting in colour change of the composite fibres from purple to navy blue/black even under low concentrations of DA. The probe was also selective to DA since the colour remained unchanged in the presence of commonly encountered interfering species such as ascorbic acid, uric acid, catechol, epinephrine and norepinephrine. Moreover, the colour change was observed rapid, occurring either immediately on contact with higher concentrations (5 x10−4 M) or within about 3−5 min for the lower concentrations (e.g. 5 x10−7 M). Since this probe does not require the use of any instruments, and is both rapid and stable over time, it can be applied in the field by an inexperienced person.
- Full Text:
- Date Issued: 2015
- Authors: Ngomane, Nokuthula , Torto, Nelson , Krause, Rui W M , Vilakazi, Sibulelo
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195407 , vital:45562 , xlink:href="https://doi.org/10.1016/j.matpr.2015.08.036"
- Description: An easily prepared solid state colorimetric probe for detecting the neurotransmitter dopamine (DA) was developed. The probe, in the form of an electrospun Nylon−6 (N6) nanofibre with embedded un−functionalized gold nanoparticles (UF−AuNPs) produces a clear colour change in the presence of a DA that is detectable by the naked eye. Characterisation of the nanofibre using UV/vis spectroscopy and electron microscopy (TEM) confirmed the formation of the AuNPs in the polymer solution, and that the AuNPs were completely encapsulated within the composite nanofibres before exposure to the analytes. The probe exhibited very high sensitivity towards DA resulting in colour change of the composite fibres from purple to navy blue/black even under low concentrations of DA. The probe was also selective to DA since the colour remained unchanged in the presence of commonly encountered interfering species such as ascorbic acid, uric acid, catechol, epinephrine and norepinephrine. Moreover, the colour change was observed rapid, occurring either immediately on contact with higher concentrations (5 x10−4 M) or within about 3−5 min for the lower concentrations (e.g. 5 x10−7 M). Since this probe does not require the use of any instruments, and is both rapid and stable over time, it can be applied in the field by an inexperienced person.
- Full Text:
- Date Issued: 2015
Meso-and axially-modified IrIIItriarylcorroles with tunable electrocatalytic properties
- Zhang, Xifeng, Wang, Yu, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Liang, Xu
- Authors: Zhang, Xifeng , Wang, Yu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190851 , vital:45034 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: The synthesis of three A2B type Ir(III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties and three A3 type IrIIItriphenylcorroles with differing pyridine axial ligands is reported, along with their structural characterization. An analysis of the structure-property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy and electrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type IrIIItriarylcorroles are highly efficient electrocatalyzed oxygen reduction reactions (ORRs) and that their reactivity can be modulated by modulating the electronic structure by changing the nature of the meso-substituent at the B-positions, and even axial pyridine ligands.
- Full Text:
- Date Issued: 2015
- Authors: Zhang, Xifeng , Wang, Yu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190851 , vital:45034 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: The synthesis of three A2B type Ir(III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties and three A3 type IrIIItriphenylcorroles with differing pyridine axial ligands is reported, along with their structural characterization. An analysis of the structure-property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy and electrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type IrIIItriarylcorroles are highly efficient electrocatalyzed oxygen reduction reactions (ORRs) and that their reactivity can be modulated by modulating the electronic structure by changing the nature of the meso-substituent at the B-positions, and even axial pyridine ligands.
- Full Text:
- Date Issued: 2015