Optical nonlinearities and photophysicochemical behaviour of green and blue forms of lutetium bisphthalocyanines
- Sekhosana, Kutloana Edith, Amuhaya, Edith, Mack, John, Nyokong, Tebello
- Authors: Sekhosana, Kutloana Edith , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241606 , vital:50954 , xlink:href="https://doi.org/10.1039/C4TC00505H"
- 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.
- Full Text:
- Date Issued: 2014
- Authors: Sekhosana, Kutloana Edith , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241606 , vital:50954 , xlink:href="https://doi.org/10.1039/C4TC00505H"
- 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.
- Full Text:
- Date Issued: 2014
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
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241459 , vital:50941 , xlink:href="https://doi.org/10.1016/j.poly.2014.07.025"
- 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.
- Full Text:
- Date Issued: 2014
- Authors: Mkhize, Colin , Britton, Jonathan , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241459 , vital:50941 , xlink:href="https://doi.org/10.1016/j.poly.2014.07.025"
- 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.
- Full Text:
- Date Issued: 2014
Characterization of electrodes modified by one pot or step by step electro-click reaction and axial ligation of iron tetracarboxyphthalocyanine
- Maringa, Audacity, Mashazi, Philani N, Nyokong, Tebello
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193892 , vital:45403 , xlink:href="https://doi.org/10.1016/j.electacta.2014.09.011"
- Description: The modification of the glassy carbon electrode (GCE) was carried out using two methods. The first method is simultaneous electropolymerization and electro-click followed by immersion into a solution of dimethyl formamide (DMF) containing FeTCPc. The second method is step by step whereby electropolymerization is carried out first followed by electro-click and then immersion into a DMF solution containing FeTCPc. From the electrochemical characterization, it was observed that the second route (step by step method) was the best as indicated by the ferricyanide studies (cyclic voltammetry and scanning electrochemical microscopy). In the electrooxidation of hydrazine, we obtained a potential of 0.26 V. Of interest were the detection limit of 6.4 μM and the catalytic rate constant of 2.1 × 109 cm3 mol−1 s−1. This shows that the sensor can be used for the electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2014
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193892 , vital:45403 , xlink:href="https://doi.org/10.1016/j.electacta.2014.09.011"
- Description: The modification of the glassy carbon electrode (GCE) was carried out using two methods. The first method is simultaneous electropolymerization and electro-click followed by immersion into a solution of dimethyl formamide (DMF) containing FeTCPc. The second method is step by step whereby electropolymerization is carried out first followed by electro-click and then immersion into a DMF solution containing FeTCPc. From the electrochemical characterization, it was observed that the second route (step by step method) was the best as indicated by the ferricyanide studies (cyclic voltammetry and scanning electrochemical microscopy). In the electrooxidation of hydrazine, we obtained a potential of 0.26 V. Of interest were the detection limit of 6.4 μM and the catalytic rate constant of 2.1 × 109 cm3 mol−1 s−1. This shows that the sensor can be used for the electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2014
A comparative photophysicochemical study of mono substituted phthalocyanines grafted onto silica nanoparticles
- Fashina, Adebayo, Antunes, Edith M, Nyokong, Tebello
- Authors: Fashina, Adebayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193844 , vital:45399 , xlink:href="https://doi.org/10.1142/S1088424614500138"
- Description: In this study, we report on the covalent linking of carboxylic acid functionalized silica nanoparticles with zinc phthalocyanine mono-substituted non-peripherally and peripherally with either a 4-amino phenoxy (1, peripheral and 2, non-peripheral) or an amino group (3 peripheral). The grafting is achieved via the formation of an amide bond between the carboxylic acid of the silica nanoparticles and the amino group of the phthalocyanine complexes. The hybrid nanoparticles retained the amorphous nature of silica nanoparticles after conjugation. A slight decrease in fluorescence and a general improvement in triplet quantum yields compared to free Pcs were observed. Triplet lifetimes for 2-SiNPs and 3-SiNPs also improved when compared to the free phthalocyanine. The changes in singlet oxygen quantum yields upon conjugation were minimal.
- Full Text:
- Date Issued: 2014
- Authors: Fashina, Adebayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193844 , vital:45399 , xlink:href="https://doi.org/10.1142/S1088424614500138"
- Description: In this study, we report on the covalent linking of carboxylic acid functionalized silica nanoparticles with zinc phthalocyanine mono-substituted non-peripherally and peripherally with either a 4-amino phenoxy (1, peripheral and 2, non-peripheral) or an amino group (3 peripheral). The grafting is achieved via the formation of an amide bond between the carboxylic acid of the silica nanoparticles and the amino group of the phthalocyanine complexes. The hybrid nanoparticles retained the amorphous nature of silica nanoparticles after conjugation. A slight decrease in fluorescence and a general improvement in triplet quantum yields compared to free Pcs were observed. Triplet lifetimes for 2-SiNPs and 3-SiNPs also improved when compared to the free phthalocyanine. The changes in singlet oxygen quantum yields upon conjugation were minimal.
- Full Text:
- Date Issued: 2014
Optical nonlinearities in non-peripherally substituted pyridyloxy phthalocyanines
- Sanusi, Kayode, Antunes, Edith M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241618 , vital:50955 , xlink:href="https://doi.org/10.1039/C3DT52462K"
- 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.
- Full Text:
- Date Issued: 2014
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241618 , vital:50955 , xlink:href="https://doi.org/10.1039/C3DT52462K"
- 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.
- Full Text:
- Date Issued: 2014
Photophysical behavior of Zn aminophenoxy substituted phthalocyanine conjugates with carboxylic acid-coated silica nanoparticles
- Fashina, Adedayo, Antunes, Edith M, Nyokong, Tebello
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193802 , vital:45397 , xlink:href="https://doi.org/10.1016/j.molstruc.2014.04.034"
- Description: This work reports on the grafting of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally and peripherally with a 4-amino phenoxy group. The phthalocyanine dyes have free amino groups, facilitating covalent attachment of the dyes on the silica surface via amide bond formation. The surface area of the functionalized silica nanoparticles increased on conjugation but the pore volumes were reduced. The phthalocyanine functionalized silica nanoparticles showed lower fluorescence quantum yields as well as shorter triplet lifetimes compared to the free phthalocyanines in dimethyl formamide. For the non-peripherally substituted phthalocyanines increases in triplet yield quantum yields, lifetimes, and singlet oxygen quantum yields were observed.
- Full Text:
- Date Issued: 2014
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193802 , vital:45397 , xlink:href="https://doi.org/10.1016/j.molstruc.2014.04.034"
- Description: This work reports on the grafting of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally and peripherally with a 4-amino phenoxy group. The phthalocyanine dyes have free amino groups, facilitating covalent attachment of the dyes on the silica surface via amide bond formation. The surface area of the functionalized silica nanoparticles increased on conjugation but the pore volumes were reduced. The phthalocyanine functionalized silica nanoparticles showed lower fluorescence quantum yields as well as shorter triplet lifetimes compared to the free phthalocyanines in dimethyl formamide. For the non-peripherally substituted phthalocyanines increases in triplet yield quantum yields, lifetimes, and singlet oxygen quantum yields were observed.
- Full Text:
- Date Issued: 2014
Conjugates of platinum nanoparticles with gallium tetra–(4-Carboxyphenyl) porphyrin and their use in photodynamic antimicrobial chemotherapy when in solution or embedded in electrospun fiber
- Managa, Muthumuni, Antunes, Edith M, Nyokong, Tebello
- Authors: Managa, Muthumuni , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193791 , vital:45396 , xlink:href="https://doi.org/10.1016/j.poly.2014.03.050"
- Description: The conjugation of Pt nanoparticles with ClGa(III) 5,10,15,20-tetrakis-(4-carboxyphenyl) porphyrin (ClGaTCPP) showed greater antimicrobial activity against a gram positive and drug resistant bacteria Staphylococcus aureus, than when the porphyrin was used alone. ClGaTCPP and its conjugate with platinum nanoparticle was successfully electrospun into a polystyrene polymer where the diameter ranged from 10 to 22 μm. The conjugates within the fiber still showed activity towards S. aureus.
- Full Text:
- Date Issued: 2014
- Authors: Managa, Muthumuni , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193791 , vital:45396 , xlink:href="https://doi.org/10.1016/j.poly.2014.03.050"
- Description: The conjugation of Pt nanoparticles with ClGa(III) 5,10,15,20-tetrakis-(4-carboxyphenyl) porphyrin (ClGaTCPP) showed greater antimicrobial activity against a gram positive and drug resistant bacteria Staphylococcus aureus, than when the porphyrin was used alone. ClGaTCPP and its conjugate with platinum nanoparticle was successfully electrospun into a polystyrene polymer where the diameter ranged from 10 to 22 μm. The conjugates within the fiber still showed activity towards S. aureus.
- Full Text:
- Date Issued: 2014
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
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241573 , vital:50951 , xlink:href="https://doi.org/10.1016/j.electacta.2013.12.132"
- 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.
- Full Text:
- Date Issued: 2014
- Authors: Maringa, Audacity , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241573 , vital:50951 , xlink:href="https://doi.org/10.1016/j.electacta.2013.12.132"
- 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.
- Full Text:
- Date Issued: 2014
Polyamide nanofiber membranes functionalized with zinc phthalocyanines
- Goethals, Annelies, Mugadza, Tawanda, Arslanoglu, Yasin, Zugle, Ruphino, Antunes, Edith M, Van Hulle, Stijn W, Nyokong, Tebello, De Clerck, Karen
- Authors: Goethals, Annelies , Mugadza, Tawanda , Arslanoglu, Yasin , Zugle, Ruphino , Antunes, Edith M , Van Hulle, Stijn W , Nyokong, Tebello , De Clerck, Karen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241505 , vital:50945 , xlink:href="https://doi.org/10.1002/app.40486"
- 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.
- Full Text:
- Date Issued: 2014
- Authors: Goethals, Annelies , Mugadza, Tawanda , Arslanoglu, Yasin , Zugle, Ruphino , Antunes, Edith M , Van Hulle, Stijn W , Nyokong, Tebello , De Clerck, Karen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241505 , vital:50945 , xlink:href="https://doi.org/10.1002/app.40486"
- 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.
- Full Text:
- Date Issued: 2014
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
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193860 , vital:45400 , xlink:href="https://doi.org/10.1016/j.dyepig.2013.12.019"
- 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.
- Full Text:
- Date Issued: 2014
- Authors: Khoza, Phindile , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193860 , vital:45400 , xlink:href="https://doi.org/10.1016/j.dyepig.2013.12.019"
- 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.
- Full Text:
- Date Issued: 2014
Photophysical properties of a new water soluble tetra thiamine substituted zinc phthalocyanine conjugated to gold nanorods of different aspect ratios
- Mthethwa, Thandekile, Antunes, Edith M, Nyokong, Tebello
- Authors: Mthethwa, Thandekile , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241583 , vital:50952 , xlink:href="https://doi.org/10.1039/C4DT00197D"
- Description: A water soluble zinc phthalocyanine substituted with thiamine is reported in this work. The aggregation of this compound in aqueous solutions causes quenching of the fluorescence quantum yields. Gold nanospheres and nanorods were linked to the phthalocyanine. X-ray photoelectron spectroscopy showed that both the amine and the sulphur groups on the thiamine substituent of the zinc phthalocyanine were involved in the linking to gold nanoparticles. The Pc showed an increase in the fluorescence quantum yields in the presence of the nanoparticles. The singlet oxygen quantum yield increased when the Pc was conjugated to the nanoparticles and even higher for larger aspect ratio gold nanorods.
- Full Text:
- Date Issued: 2014
- Authors: Mthethwa, Thandekile , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241583 , vital:50952 , xlink:href="https://doi.org/10.1039/C4DT00197D"
- Description: A water soluble zinc phthalocyanine substituted with thiamine is reported in this work. The aggregation of this compound in aqueous solutions causes quenching of the fluorescence quantum yields. Gold nanospheres and nanorods were linked to the phthalocyanine. X-ray photoelectron spectroscopy showed that both the amine and the sulphur groups on the thiamine substituent of the zinc phthalocyanine were involved in the linking to gold nanoparticles. The Pc showed an increase in the fluorescence quantum yields in the presence of the nanoparticles. The singlet oxygen quantum yield increased when the Pc was conjugated to the nanoparticles and even higher for larger aspect ratio gold nanorods.
- Full Text:
- Date Issued: 2014
Photophysicochemical behavior and antimicrobial activity of dihydroxosilicon tris (diaquaplatinum) octacarboxyphthalocyanine
- Managa, Muthumuni, Idowu, Mopelola A, Antunes, Edith M, Nyokong, Tebello
- Authors: Managa, Muthumuni , Idowu, Mopelola A , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241527 , vital:50947 , xlink:href="https://doi.org/10.1016/j.saa.2014.01.087"
- Description: Platination of dihydroxosilicon octacarboxyphthalocyanine (OH)2SiOCPc was successfully carried out to give dihydroxosilicon tris(diaquaplatinum)octacarboxyphthalocyanine (OH)2SiOCPc(Pt)3 conjugate. Slight blue shifting of the absorption spectrum of (OH)2SiOCPc(Pt)3 was observed on conjugation with platinum. Comparative photophysicochemical behavior and antimicrobial photo-activities of (OH)2SiOCPc(Pt)3 conjugate with (OH)2SiOCPc or Pt nanoparticles revealed that the heavy atom, Pt on the periphery of the phthalocyanine significantly enhanced its singlet oxygen generation with a quantum yield of 0.56 obtained for the (OH)2SiOCPc(Pt)3 conjugate. The (OH)2SiOCPc(Pt)3 conjugate showed highest antimicrobial activity towards Candida albicans and Escherichia coli compared to (OH)2SiOCPc and Pt nanoparticles alone under illumination.
- Full Text:
- Date Issued: 2014
- Authors: Managa, Muthumuni , Idowu, Mopelola A , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241527 , vital:50947 , xlink:href="https://doi.org/10.1016/j.saa.2014.01.087"
- Description: Platination of dihydroxosilicon octacarboxyphthalocyanine (OH)2SiOCPc was successfully carried out to give dihydroxosilicon tris(diaquaplatinum)octacarboxyphthalocyanine (OH)2SiOCPc(Pt)3 conjugate. Slight blue shifting of the absorption spectrum of (OH)2SiOCPc(Pt)3 was observed on conjugation with platinum. Comparative photophysicochemical behavior and antimicrobial photo-activities of (OH)2SiOCPc(Pt)3 conjugate with (OH)2SiOCPc or Pt nanoparticles revealed that the heavy atom, Pt on the periphery of the phthalocyanine significantly enhanced its singlet oxygen generation with a quantum yield of 0.56 obtained for the (OH)2SiOCPc(Pt)3 conjugate. The (OH)2SiOCPc(Pt)3 conjugate showed highest antimicrobial activity towards Candida albicans and Escherichia coli compared to (OH)2SiOCPc and Pt nanoparticles alone under illumination.
- Full Text:
- Date Issued: 2014
Synthesis, photophysicochemical properties and TD-DFT calculations of tetrakis (2-benzoyl-4-chlorophenoxy) phthalocyanines
- Yilmaz, Yusuf, Mack, John, Sener, M Kasim, Sönmez, Mehmet, Nyokong, Tebello
- Authors: Yilmaz, Yusuf , Mack, John , Sener, M Kasim , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241538 , vital:50948 , xlink:href="https://doi.org/10.1142/S1088424614500047"
- Description: The synthesis of metal free, magnesium and zinc tetrakis(2-benzoyl-4-chlorophenoxy) phthalocyanine derivatives (2–4) is described along with their characterization by elemental analysis, IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. Trends observed in the fluorescence, triplet state, singlet oxygen and photodegradation quantum yields and the triplet state lifetimes are also analyzed. The compounds exhibit high solubility in a wide range of organic solvents and no evidence of aggregation was observed over a wide concentration range. The Zn(II) complex (4) was found to have a very high singlet oxygen quantum yield (ΦΔ = 0.78) in dimethylsulfoxide (DMSO) and a reasonably large triplet state quantum yield (ΦT = 0.82). The photophysical and photochemical properties clearly demonstrate that these compounds could prove useful in singlet oxygen applications such as photodynamic therapy (PDT). DFT and TD-DFT calculations were used to assess the impact of the positional isomerism of the 2-benzoyl-4-chlorophenoxy substituents on the electronic structures and optical spectroscopy.
- Full Text:
- Date Issued: 2014
- Authors: Yilmaz, Yusuf , Mack, John , Sener, M Kasim , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241538 , vital:50948 , xlink:href="https://doi.org/10.1142/S1088424614500047"
- Description: The synthesis of metal free, magnesium and zinc tetrakis(2-benzoyl-4-chlorophenoxy) phthalocyanine derivatives (2–4) is described along with their characterization by elemental analysis, IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. Trends observed in the fluorescence, triplet state, singlet oxygen and photodegradation quantum yields and the triplet state lifetimes are also analyzed. The compounds exhibit high solubility in a wide range of organic solvents and no evidence of aggregation was observed over a wide concentration range. The Zn(II) complex (4) was found to have a very high singlet oxygen quantum yield (ΦΔ = 0.78) in dimethylsulfoxide (DMSO) and a reasonably large triplet state quantum yield (ΦT = 0.82). The photophysical and photochemical properties clearly demonstrate that these compounds could prove useful in singlet oxygen applications such as photodynamic therapy (PDT). DFT and TD-DFT calculations were used to assess the impact of the positional isomerism of the 2-benzoyl-4-chlorophenoxy substituents on the electronic structures and optical spectroscopy.
- Full Text:
- Date Issued: 2014
Trends in the TD-DFT calculations of porphyrin and phthalocyanine analogs
- Mack, John, Stone, Justin, Nyokong, Tebello
- Authors: Mack, John , Stone, Justin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193882 , vital:45402 , xlink:href="https://doi.org/10.1142/S108842461450045X"
- Description: In 2005, Kobayashi and coworkers reported trends in the TD-DFT spectra of 17 Zn (II) porphyrinoids [J. Am. Chem. Soc. 2005; 127: 17697] that were analyzed using Michl's perimeter model as part of a study of the anomalous magnetic circular dichroism (MCD) spectroscopy of zinc tetraphenyltetraacenaphthoporphyrin. In recent years, it has become increasingly clear that TD-DFT calculations with the commonly used hybrid B3LYP exchange-correlation functional of the Gaussian software package are problematic in the B-band region of porphyrinoid spectra, since the degree of configurational interaction between the B and higher energy ππ* state appears to be significantly overestimated. The CAM-B3LYP functional is now often preferred for analyzing the optical properties of porphyrinoids, since it includes a long-range correction of the exchange potential, which incorporates an increasing fraction of Hartree–Fock (HF) exchange as the interelectronic separation increases, making it better suited for studying compounds where there is significant charge transfer in the electronic excited states. The trends in the TD-DFT calculations are reexamined with a wider range porphyrinoid compounds including several with pyrazino moieties and are found to provide a closer agreement with the experimental in the B-band region for complexes such as zinc tetraphenylporphyrin and phthalocyanine.
- Full Text:
- Date Issued: 2014
- Authors: Mack, John , Stone, Justin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193882 , vital:45402 , xlink:href="https://doi.org/10.1142/S108842461450045X"
- Description: In 2005, Kobayashi and coworkers reported trends in the TD-DFT spectra of 17 Zn (II) porphyrinoids [J. Am. Chem. Soc. 2005; 127: 17697] that were analyzed using Michl's perimeter model as part of a study of the anomalous magnetic circular dichroism (MCD) spectroscopy of zinc tetraphenyltetraacenaphthoporphyrin. In recent years, it has become increasingly clear that TD-DFT calculations with the commonly used hybrid B3LYP exchange-correlation functional of the Gaussian software package are problematic in the B-band region of porphyrinoid spectra, since the degree of configurational interaction between the B and higher energy ππ* state appears to be significantly overestimated. The CAM-B3LYP functional is now often preferred for analyzing the optical properties of porphyrinoids, since it includes a long-range correction of the exchange potential, which incorporates an increasing fraction of Hartree–Fock (HF) exchange as the interelectronic separation increases, making it better suited for studying compounds where there is significant charge transfer in the electronic excited states. The trends in the TD-DFT calculations are reexamined with a wider range porphyrinoid compounds including several with pyrazino moieties and are found to provide a closer agreement with the experimental in the B-band region for complexes such as zinc tetraphenylporphyrin and phthalocyanine.
- Full Text:
- Date Issued: 2014
Photophysicochemical properties and TD-DFT calculations of a novel terminal alkyne substituted metal free phthalocyanine
- Yilmaz, Yusuf, Mack, John, Sönmez, Mehmet, Nyokong, Tebello
- Authors: Yilmaz, Yusuf , Mack, John , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241562 , vital:50950 , xlink:href="https://doi.org/10.1142/S1088424613501241"
- Description: The synthesis of a novel free base tetrakis(prop-2-ynyloxy)phthalocyanine (2) is described, along with its characterization by IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. The compound exhibited good solubility in a wide range of organic solvents and no significant aggregation was observed over a wide concentration range. The values for the singlet oxygen (ΦΔ), photodegradation, fluorescence (ΦF) and triplet state quantum yields and the fluorescence and triplet state lifetimes are reported. A relatively high ΦΔ value of 0.46 was obtained in DMSO. The ability to carry out "click" chemistry at the ligand periphery enhances the potential utility of 2 for use in bioconjugates in photodynamic therapy (PDT). A moderately high ΦF value of 0.18 is observed for emission in the therapeutic window in the near-IR region, which suggests that it may also be possible to determine the level of localization of 2 in tumor cells through bioimaging.
- Full Text:
- Date Issued: 2014
- Authors: Yilmaz, Yusuf , Mack, John , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241562 , vital:50950 , xlink:href="https://doi.org/10.1142/S1088424613501241"
- Description: The synthesis of a novel free base tetrakis(prop-2-ynyloxy)phthalocyanine (2) is described, along with its characterization by IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. The compound exhibited good solubility in a wide range of organic solvents and no significant aggregation was observed over a wide concentration range. The values for the singlet oxygen (ΦΔ), photodegradation, fluorescence (ΦF) and triplet state quantum yields and the fluorescence and triplet state lifetimes are reported. A relatively high ΦΔ value of 0.46 was obtained in DMSO. The ability to carry out "click" chemistry at the ligand periphery enhances the potential utility of 2 for use in bioconjugates in photodynamic therapy (PDT). A moderately high ΦF value of 0.18 is observed for emission in the therapeutic window in the near-IR region, which suggests that it may also be possible to determine the level of localization of 2 in tumor cells through bioimaging.
- Full Text:
- Date Issued: 2014
Synthesis, characterization and photodynamic therapy properties of an octa-4-tert-butylphenoxy-substituted phosphorus (V) triazatetrabenzcorrole
- Shi, Maohu, Tian, Jiangwei, Mkhize, Colin, Kubheka, Gugu, Zhou, Jinfeng, Mack, John, Nyokong, Tebello, Shen, Zhen
- Authors: Shi, Maohu , Tian, Jiangwei , Mkhize, Colin , Kubheka, Gugu , Zhou, Jinfeng , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241494 , vital:50944 , xlink:href="https://doi.org/10.1142/S1088424614500436"
- Description: A novel octa-4-tert-butylphenoxy-substituted phosphorus(V) triazatetrabenzcorrole (PVTBC), has been synthesized and characterized by MALDI-TOF MS and NMR, FT-IR and MCD spectroscopy. The fluorescence emission spectrum was used to determine the fluorescence quantum yield and the quantum yield for singlet oxygen generation was calculated by using 1,3-diphenylisobenzofuran as a scavenger. The photocytoxicity against U87MG cells was measured. The results indicated that PVTBC is potentially useful as an NIR region photosensitizer for photodynamic therapy (PDT).
- Full Text:
- Date Issued: 2014
- Authors: Shi, Maohu , Tian, Jiangwei , Mkhize, Colin , Kubheka, Gugu , Zhou, Jinfeng , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241494 , vital:50944 , xlink:href="https://doi.org/10.1142/S1088424614500436"
- Description: A novel octa-4-tert-butylphenoxy-substituted phosphorus(V) triazatetrabenzcorrole (PVTBC), has been synthesized and characterized by MALDI-TOF MS and NMR, FT-IR and MCD spectroscopy. The fluorescence emission spectrum was used to determine the fluorescence quantum yield and the quantum yield for singlet oxygen generation was calculated by using 1,3-diphenylisobenzofuran as a scavenger. The photocytoxicity against U87MG cells was measured. The results indicated that PVTBC is potentially useful as an NIR region photosensitizer for photodynamic therapy (PDT).
- Full Text:
- Date Issued: 2014
Enhanced optical limiting performance in phthalocyanine-quantum dot nanocomposites by free-carrier absorption mechanism
- Sanusi, Kayode, Khene, Samson M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Khene, Samson M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193904 , vital:45404 , xlink:href="https://doi.org/10.1016/j.optmat.2014.07.024"
- Description: Enhanced nonlinear optical properties (in dimethyl sulphoxide) is observed for 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (InPc) when covalently linked to CdSe/ZnS or CdSe quantum dots (QDs). The experimental nonlinear optical parameters were obtained from Z-Scan measurements. Contributions from two-photon absorption (2PA) due to the InPc, and free-carrier absorption (FCA) by QDS have been identified as the main factors responsible for the enhanced optical limiting. The effective nonlinear absorption coefficient for InPc-CdSe/ZnS was found to be 700.0 cm/GW. The FCA cross-sections for InPc-CdSe/ZnS and InPc-CdSe composites were found to be 1.52 × 10−19 and 6.00 × 10−20 cm2 respectively. A much lower limiting threshold of 92 mJ cm−2 was observed for InPc-CdSe/ZnS nanocomposite, hence, making it suitable for use as optical limiting material. Density Functional Theory (DFT) calculations on similar phthalocyanine-quantum dots system was modeled in order to explain the enhancement in the observed nonlinear optical properties of the Pc in the presence of the QDs. The experimentally determined nonlinear optical properties are well within the range of the DFT calculated properties.
- Full Text:
- Date Issued: 2014
- Authors: Sanusi, Kayode , Khene, Samson M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193904 , vital:45404 , xlink:href="https://doi.org/10.1016/j.optmat.2014.07.024"
- Description: Enhanced nonlinear optical properties (in dimethyl sulphoxide) is observed for 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (InPc) when covalently linked to CdSe/ZnS or CdSe quantum dots (QDs). The experimental nonlinear optical parameters were obtained from Z-Scan measurements. Contributions from two-photon absorption (2PA) due to the InPc, and free-carrier absorption (FCA) by QDS have been identified as the main factors responsible for the enhanced optical limiting. The effective nonlinear absorption coefficient for InPc-CdSe/ZnS was found to be 700.0 cm/GW. The FCA cross-sections for InPc-CdSe/ZnS and InPc-CdSe composites were found to be 1.52 × 10−19 and 6.00 × 10−20 cm2 respectively. A much lower limiting threshold of 92 mJ cm−2 was observed for InPc-CdSe/ZnS nanocomposite, hence, making it suitable for use as optical limiting material. Density Functional Theory (DFT) calculations on similar phthalocyanine-quantum dots system was modeled in order to explain the enhancement in the observed nonlinear optical properties of the Pc in the presence of the QDs. The experimentally determined nonlinear optical properties are well within the range of the DFT calculated properties.
- Full Text:
- Date Issued: 2014
Effects of redox mediators on the catalytic activity of iron porphyrins towards oxygen reduction in acidic media
- He, Qinggang, Wu, Gang, Liu, Ke, Khene, Samson M, Li, Qing, Mugadza, Tawanda, Deunf, Elise, Nyokong, Tebello, Chen, Shaowei W
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated.
- Full Text:
- Date Issued: 2014
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated.
- Full Text:
- Date Issued: 2014