Indium phthalocyanines
- Pinar, Sen, Mack, John, Nyokong, Tebello
- Authors: Pinar, Sen , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229998 , vital:49731 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.131850"
- Description: In this study, the photodynamic antimicrobial activities of a series of new tetra-substituted indium phthalocyanine (InPc) complexes are assessed. An aldehyde substituted complex (2) was initially prepared, which was converted through a condensatioreaction to an imine-pyrrolidine substituted complex (3), which in turn was quaternized to form a tetracationic species (4). Favorable photophysicochemical properties were obtained by incorporating a heavy In(III) ion into the central cavity. Aggregation studies revealed that 2–4 remain non-aggregated in DMSO at concentration below 25 µM. The photodeactivation of S.aureus and E.coli was studied. Log reduction values > 9.0 were obtained for cationic InPc 4 after 30 min of incubation and exposure to light for 75 min.
- Full Text:
- Date Issued: 2022
- Authors: Pinar, Sen , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229998 , vital:49731 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.131850"
- Description: In this study, the photodynamic antimicrobial activities of a series of new tetra-substituted indium phthalocyanine (InPc) complexes are assessed. An aldehyde substituted complex (2) was initially prepared, which was converted through a condensatioreaction to an imine-pyrrolidine substituted complex (3), which in turn was quaternized to form a tetracationic species (4). Favorable photophysicochemical properties were obtained by incorporating a heavy In(III) ion into the central cavity. Aggregation studies revealed that 2–4 remain non-aggregated in DMSO at concentration below 25 µM. The photodeactivation of S.aureus and E.coli was studied. Log reduction values > 9.0 were obtained for cationic InPc 4 after 30 min of incubation and exposure to light for 75 min.
- Full Text:
- Date Issued: 2022
A heavy-atom-free π-extended N-confused porphyrin as a photosensitizer for photodynamic therapy
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185909 , vital:44447 , xlink:href="https://doi.org/10.1039/d1nj00112d"
- Description: The synthesis and characterization of a novel 1,3-diethyl-2-thiobarbituric-acid-substituted N-confused porphyrin (NCP-TB) is reported, along with a study of its photodynamic activity against MCF-7 cells using 530 (110 mW cm−2) and 660 nm (280 mW cm−2) Thorlabs light-emitting diodes for 30 min. The singlet oxygen quantum yield for NCP-TB is 0.38 compared to 0.23 for the parent unsubstituted N-confused porphyrin (NCP) due to the presence of a sulfur atom. NCP-TB exhibits enhanced PDT activity compared to NCP at both wavelengths. A significantly lower IC50 value of 5.2 μM was obtained at 530 nm (14.7 μM at 660 nm) despite a smaller light dose, due to a large red shift of the intense B band into the green region of the spectrum. 2′,7′-Dichlorofluorescein diacetate (DCFDA) assays demonstrate that there is intracellular generation of reactive oxygen species upon exposure to light.
- Full Text:
- Date Issued: 2021
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185909 , vital:44447 , xlink:href="https://doi.org/10.1039/d1nj00112d"
- Description: The synthesis and characterization of a novel 1,3-diethyl-2-thiobarbituric-acid-substituted N-confused porphyrin (NCP-TB) is reported, along with a study of its photodynamic activity against MCF-7 cells using 530 (110 mW cm−2) and 660 nm (280 mW cm−2) Thorlabs light-emitting diodes for 30 min. The singlet oxygen quantum yield for NCP-TB is 0.38 compared to 0.23 for the parent unsubstituted N-confused porphyrin (NCP) due to the presence of a sulfur atom. NCP-TB exhibits enhanced PDT activity compared to NCP at both wavelengths. A significantly lower IC50 value of 5.2 μM was obtained at 530 nm (14.7 μM at 660 nm) despite a smaller light dose, due to a large red shift of the intense B band into the green region of the spectrum. 2′,7′-Dichlorofluorescein diacetate (DCFDA) assays demonstrate that there is intracellular generation of reactive oxygen species upon exposure to light.
- Full Text:
- Date Issued: 2021
Light-driven antimicrobial therapy of palladium porphyrins and their chitosan immobilization derivatives and their photophysical-chemical properties
- Sen, Pinar, Soy, Rodah, Mgidlana, Sithi, Mack, John, Nyokong, Tebello
- Authors: Sen, Pinar , Soy, Rodah , Mgidlana, Sithi , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300112 , vital:57894 , xlink:href="https://doi.org/10.1016/j.dyepig.2022.110313"
- Description: The emergence of antimicrobial resistance has made the development of photodynamic therapy (PDT) related applications essential, since microorganisms can not form resistance to this method. Porphyrins are well-known photosensitizers for PDT related applications. Thus, the present study outlines the synthesis, characterization and evaluation of the utility of palladium porphyrins and their chitosan inclusion complexes as photosensitizer dye in photodynamic antimicrobial therapy (PACT). Before in vitro cell studies, the photophysical-chemical studies of all obtained structures were performed in solution. It was observed that the immobilization of the porphyrins into the chitosan influenced the photophysical-chemical and PACT activity properties. The determined fluorescence quantum yield was very low, in the range of 0.007–0.028 for all samples indicating the efficient triplet state population to cause high singlet oxygen quantum yield (ΦΔ). The measured ΦΔ values were in the range of 0.51–0.61 for the porphyrins and 0.53–0.66 for porphyrin chitosan immobilization complexes. Our results demonstrate that the PACT activity of cationic porphyrin (P3) and its chitosan immobilization form (P3-Ct) were more efficient in decreasing the number of viable cells up to 100% in vitro.
- Full Text:
- Date Issued: 2022
- Authors: Sen, Pinar , Soy, Rodah , Mgidlana, Sithi , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300112 , vital:57894 , xlink:href="https://doi.org/10.1016/j.dyepig.2022.110313"
- Description: The emergence of antimicrobial resistance has made the development of photodynamic therapy (PDT) related applications essential, since microorganisms can not form resistance to this method. Porphyrins are well-known photosensitizers for PDT related applications. Thus, the present study outlines the synthesis, characterization and evaluation of the utility of palladium porphyrins and their chitosan inclusion complexes as photosensitizer dye in photodynamic antimicrobial therapy (PACT). Before in vitro cell studies, the photophysical-chemical studies of all obtained structures were performed in solution. It was observed that the immobilization of the porphyrins into the chitosan influenced the photophysical-chemical and PACT activity properties. The determined fluorescence quantum yield was very low, in the range of 0.007–0.028 for all samples indicating the efficient triplet state population to cause high singlet oxygen quantum yield (ΦΔ). The measured ΦΔ values were in the range of 0.51–0.61 for the porphyrins and 0.53–0.66 for porphyrin chitosan immobilization complexes. Our results demonstrate that the PACT activity of cationic porphyrin (P3) and its chitosan immobilization form (P3-Ct) were more efficient in decreasing the number of viable cells up to 100% in vitro.
- Full Text:
- Date Issued: 2022
Integrated photocatalyst adsorbents based on porphyrin anchored to activated carbon granules for water treatment
- Oyim, James, Amuhaya, Edith, Matshitse, Refilwe, Mack, John, Nyokong, Tebello
- Authors: Oyim, James , Amuhaya, Edith , Matshitse, Refilwe , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300101 , vital:57893 , xlink:href="https://doi.org/10.1016/j.cartre.2022.100191"
- Description: Integration of adsorption and photocatalysis processes can lead to several benefits in water treatment. Integrating well-known adsorbents with photocatalysts ensures that all the interesting components are preserved and helps to overcome the serious downsides of each material and technique when operated independently. In this work, we introduce a new concept of combining both absorption and photodegradation mechanisms using organic photocatalytic adsorbents for water purification. This was achieved by formulating photosensitizing hybrids based on a newly synthesized chloroindium (III) 5,10,15,20-tetrakis(4-acetamidophenyl) porphyrin (InTAAP) compound, anchored on oxygen functionalized coconut shell-based activated carbon granules supports. The fashioned integrated photocatalyst adsorbent hybrid (InTAAP(ACO)) was then studied for their adsorption and photodegradation efficiency using methylene blue dye, where InTAAP(ACO) showed excellent photocatalytic activity compared to ACO and unfunctionalized activated carbon granules (AC), with appreciably high and adsorption properties as AC and ACO.
- Full Text:
- Date Issued: 2022
- Authors: Oyim, James , Amuhaya, Edith , Matshitse, Refilwe , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300101 , vital:57893 , xlink:href="https://doi.org/10.1016/j.cartre.2022.100191"
- Description: Integration of adsorption and photocatalysis processes can lead to several benefits in water treatment. Integrating well-known adsorbents with photocatalysts ensures that all the interesting components are preserved and helps to overcome the serious downsides of each material and technique when operated independently. In this work, we introduce a new concept of combining both absorption and photodegradation mechanisms using organic photocatalytic adsorbents for water purification. This was achieved by formulating photosensitizing hybrids based on a newly synthesized chloroindium (III) 5,10,15,20-tetrakis(4-acetamidophenyl) porphyrin (InTAAP) compound, anchored on oxygen functionalized coconut shell-based activated carbon granules supports. The fashioned integrated photocatalyst adsorbent hybrid (InTAAP(ACO)) was then studied for their adsorption and photodegradation efficiency using methylene blue dye, where InTAAP(ACO) showed excellent photocatalytic activity compared to ACO and unfunctionalized activated carbon granules (AC), with appreciably high and adsorption properties as AC and ACO.
- Full Text:
- Date Issued: 2022
Low-Symmetry Phthalocyanines Bearing Carboxy-Groups
- Bunin, Dmitry A, Ndebele, Nobuhle, Martynov, Alexander G, Mack, John, Gorbunova, Yulia G, Nyokong, Tebello
- Authors: Bunin, Dmitry A , Ndebele, Nobuhle , Martynov, Alexander G , Mack, John , Gorbunova, Yulia G , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231262 , vital:49870 , xlink:href="https://doi.org/10.3390/molecules27020524" "
- Description: The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.
- Full Text:
- Date Issued: 2022
- Authors: Bunin, Dmitry A , Ndebele, Nobuhle , Martynov, Alexander G , Mack, John , Gorbunova, Yulia G , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231262 , vital:49870 , xlink:href="https://doi.org/10.3390/molecules27020524" "
- Description: The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.
- Full Text:
- Date Issued: 2022
A Sn (iv) porphyrin with mitochondria targeting properties for enhanced photodynamic activity against MCF-7 cells
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230897 , vital:49829 , xlink:href="https://doi.org/10.1039/D2NJ00350C"
- Description: Two readily synthesized Sn(IV) porphyrins (SnP, SnPH) have been prepared with and without the cationic triphenylphosphonium moiety (TPP+), which have high singlet oxygen quantum yields (ca. 0.72) and long triplet state lifetimes. The Sn(IV) porphyrin with a TPP+ moiety (SnPH) exhibits favorable photodynamic activity against MCF-7 cells with IC50 values of 2.9 μM. SnPH exhibits higher cellular uptake than SnP in MCF-7 cells. A Rhodamine 123 (Rh123) assay showed that SnPH targets mitochondria and induces apoptosis by generating reactive oxygen species. The results demonstrate that this structural modification strategy merits further in-depth study.
- Full Text:
- Date Issued: 2022
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230897 , vital:49829 , xlink:href="https://doi.org/10.1039/D2NJ00350C"
- Description: Two readily synthesized Sn(IV) porphyrins (SnP, SnPH) have been prepared with and without the cationic triphenylphosphonium moiety (TPP+), which have high singlet oxygen quantum yields (ca. 0.72) and long triplet state lifetimes. The Sn(IV) porphyrin with a TPP+ moiety (SnPH) exhibits favorable photodynamic activity against MCF-7 cells with IC50 values of 2.9 μM. SnPH exhibits higher cellular uptake than SnP in MCF-7 cells. A Rhodamine 123 (Rh123) assay showed that SnPH targets mitochondria and induces apoptosis by generating reactive oxygen species. The results demonstrate that this structural modification strategy merits further in-depth study.
- Full Text:
- Date Issued: 2022
Promotion of Catalytic Oxygen Reduction Reactions
- Wei, Yuqin, Zhao, Long, Yuan, Rui, Xue, Zhaoli, Mack, John, Chivumba, Choonzo, Nyokong, Tebello, Zhang, Jianming
- Authors: Wei, Yuqin , Zhao, Long , Yuan, Rui , Xue, Zhaoli , Mack, John , Chivumba, Choonzo , Nyokong, Tebello , Zhang, Jianming
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300347 , vital:57919 , xlink:href="https://doi.org/10.1021/acs.inorgchem.2c01591"
- Description: Three ABAB-type cobalt meso-tetraarylporphyrins with fluorine (F-CoPor), acetic acid (AC-CoPor), and cyanoacetic acid (CN-CoPor) groups at the para-positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the meso-aryl rings. Electrochemical measurements suggest that electrodes with CN-CoPor (CN-CoPor/C) exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the F-CoPor/C electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the meso-position is an efficient way to modify the ORR performance.
- Full Text:
- Date Issued: 2022
- Authors: Wei, Yuqin , Zhao, Long , Yuan, Rui , Xue, Zhaoli , Mack, John , Chivumba, Choonzo , Nyokong, Tebello , Zhang, Jianming
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300347 , vital:57919 , xlink:href="https://doi.org/10.1021/acs.inorgchem.2c01591"
- Description: Three ABAB-type cobalt meso-tetraarylporphyrins with fluorine (F-CoPor), acetic acid (AC-CoPor), and cyanoacetic acid (CN-CoPor) groups at the para-positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the meso-aryl rings. Electrochemical measurements suggest that electrodes with CN-CoPor (CN-CoPor/C) exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the F-CoPor/C electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the meso-position is an efficient way to modify the ORR performance.
- Full Text:
- Date Issued: 2022
Structural modification of RhIIItriarylcorroles for enhanced electrocatalyzed hydrogen evolution reactions
- Zhu, Weihua, Li, Lihua, Wang, Yu, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Liang, Xu
- Authors: Zhu, Weihua , Li, Lihua , Wang, Yu , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229933 , vital:49724 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.110046"
- Description: A series of A3 type RhIIItriarylcorroles 2a-c with different meso-substituents with differing electron-donating and withdrawing properties and two A2B type RhIIItriarylcorroles 4a-b with meso-methylthiophenyls at the B position have been prepared and characterized. An analysis of structure-property relationships of 2a-c and 4a-b has been carried out by comparing the optical spectroscopy and electrochemistry of the dyes to trends predicted in DFT and TD-DFT calculations. Rational structural modification strategies that enhance the suitability of 2a-c for use as highly efficient catalysts for hydrogen evolution reactions on glassy carbon electrodes coated with 2a-c/reduced graphene oxide composites and of 4a-b in surface-modified Au electrodes are explored.
- Full Text:
- Date Issued: 2022
- Authors: Zhu, Weihua , Li, Lihua , Wang, Yu , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229933 , vital:49724 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.110046"
- Description: A series of A3 type RhIIItriarylcorroles 2a-c with different meso-substituents with differing electron-donating and withdrawing properties and two A2B type RhIIItriarylcorroles 4a-b with meso-methylthiophenyls at the B position have been prepared and characterized. An analysis of structure-property relationships of 2a-c and 4a-b has been carried out by comparing the optical spectroscopy and electrochemistry of the dyes to trends predicted in DFT and TD-DFT calculations. Rational structural modification strategies that enhance the suitability of 2a-c for use as highly efficient catalysts for hydrogen evolution reactions on glassy carbon electrodes coated with 2a-c/reduced graphene oxide composites and of 4a-b in surface-modified Au electrodes are explored.
- Full Text:
- Date Issued: 2022
Ball-type phthalocyanines and reduced graphene oxide nanoparticles as separate and combined corrosion inhibitors of aluminium in HCl
- Nnaji, Nnaemeka, Nawji, Njemuwa, Mack, John, Nyokong, Tebello
- Authors: Nnaji, Nnaemeka , Nawji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185421 , vital:44385 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.130279"
- Description: Corrosion inhibition performances and adsorption behaviour at the aluminum-HCl solution interface were investigated for reduced graphene oxide nanosheets (rGONS), tetrakis-[4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)] (diphthalocyaninato gallium (III) chloride) (2) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium(III) chloride) (1). Corrosion inhibition effects of rGONS, 1 and 2 were evaluated alone and in combination in 1.0 M hydrochloric acid solution using electrochemical techniques. The mechanism of aluminum corrosion inhibition revealed predominantly anodic character for rGONS and predominantly cathodic character for 1, 2, and conjugates with rGONS . The polarization technique gave inhibition efficiency values of 96.5% and 96.9% respectively for 1 and 2, which increased in the presence of rGONS to 97.4% and 98.1%, respectively, for the highest concentrations of 1 and 2. Scanning electron microscopy revealed effective metal surface protection by the inhibitors by formation of protective films.
- Full Text:
- Date Issued: 2021
- Authors: Nnaji, Nnaemeka , Nawji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185421 , vital:44385 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.130279"
- Description: Corrosion inhibition performances and adsorption behaviour at the aluminum-HCl solution interface were investigated for reduced graphene oxide nanosheets (rGONS), tetrakis-[4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)] (diphthalocyaninato gallium (III) chloride) (2) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium(III) chloride) (1). Corrosion inhibition effects of rGONS, 1 and 2 were evaluated alone and in combination in 1.0 M hydrochloric acid solution using electrochemical techniques. The mechanism of aluminum corrosion inhibition revealed predominantly anodic character for rGONS and predominantly cathodic character for 1, 2, and conjugates with rGONS . The polarization technique gave inhibition efficiency values of 96.5% and 96.9% respectively for 1 and 2, which increased in the presence of rGONS to 97.4% and 98.1%, respectively, for the highest concentrations of 1 and 2. Scanning electron microscopy revealed effective metal surface protection by the inhibitors by formation of protective films.
- Full Text:
- Date Issued: 2021
Disilane-bridged architectures with high optical transparency for optical limiting
- Feng, Hongjie, Zhou, Zhikuan, May, Aviwe K, Chen, Jiaying, Mack, John, Nyokong, Tebello, Gai, Lizhi, Lu, Hua
- Authors: Feng, Hongjie , Zhou, Zhikuan , May, Aviwe K , Chen, Jiaying , Mack, John , Nyokong, Tebello , Gai, Lizhi , Lu, Hua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190623 , vital:45011 , xlink:href="https://doi.org/10.1039/D1TC01488A"
- Description: A novel tetraphenylethylene (TPE) architecture that makes use of a disilane bridge was developed to successfully prepare organic optical power limiting (OPL) materials with high transparency. The σ-bridged TPE derivatives exhibit enhanced solid-state emission efficacies up to 4 times that of TPE. Due to the unique σ-electron delocalization, the incorporated Si–Si bridge gives rise to intense nonlinear optics (NLO) properties. These compounds show favorable optical transparency in the visible region, since the σ–π interaction has a relatively minor effect on the absorption properties of TPE. The poly(bisphenol A carbonate) (PBC) thin films of disilane-bridged compounds exhibit significant reverse saturable absorbance (RSA) responses during Z-scan measurements at 532 nm. In contrast, negligible OPL properties were observed in tetrahydrofuran (THF) solution and when a PBC thin film was prepared with TPE. The disilane-bridged molecular system represents a novel and easily prepared architecture for the construction of solid-state optical limiting materials.
- Full Text:
- Date Issued: 2021
- Authors: Feng, Hongjie , Zhou, Zhikuan , May, Aviwe K , Chen, Jiaying , Mack, John , Nyokong, Tebello , Gai, Lizhi , Lu, Hua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190623 , vital:45011 , xlink:href="https://doi.org/10.1039/D1TC01488A"
- Description: A novel tetraphenylethylene (TPE) architecture that makes use of a disilane bridge was developed to successfully prepare organic optical power limiting (OPL) materials with high transparency. The σ-bridged TPE derivatives exhibit enhanced solid-state emission efficacies up to 4 times that of TPE. Due to the unique σ-electron delocalization, the incorporated Si–Si bridge gives rise to intense nonlinear optics (NLO) properties. These compounds show favorable optical transparency in the visible region, since the σ–π interaction has a relatively minor effect on the absorption properties of TPE. The poly(bisphenol A carbonate) (PBC) thin films of disilane-bridged compounds exhibit significant reverse saturable absorbance (RSA) responses during Z-scan measurements at 532 nm. In contrast, negligible OPL properties were observed in tetrahydrofuran (THF) solution and when a PBC thin film was prepared with TPE. The disilane-bridged molecular system represents a novel and easily prepared architecture for the construction of solid-state optical limiting materials.
- Full Text:
- Date Issued: 2021
A simple quinoline-thiophene Schiff base turn-off chemosensor for Hg2+ detection
- Musikavanhu, Brian, Muthusamy, Selvaraj, Zhu, Dongwei, Xue, Zhaoli, Yu, Qian, Chivumba, Choonzo N, Mack, John, Nyokong, Tebello, Wang, Shengjun, Zhao, Long
- Authors: Musikavanhu, Brian , Muthusamy, Selvaraj , Zhu, Dongwei , Xue, Zhaoli , Yu, Qian , Chivumba, Choonzo N , Mack, John , Nyokong, Tebello , Wang, Shengjun , Zhao, Long
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230362 , vital:49771 , xlink:href="https://doi.org/10.1016/j.saa.2021.120338"
- Description: A new Schiff base probe (QT) consisting of 8-aminoquinoline (Q) and thiophene-2-carboxaldehyde (T) moieties has been synthesized. QT undergoes chelation-enhanced fluorescence quenching when exposed to Hg2+ due to coordination by the sulfur and nitrogen atoms of QT thus forming a facile “turn-off” sensor. The formation of the chelation complex was confirmed by UV–visible absorption and emission spectral measurements, 1H NMR titration and density functional theory calculations. These studies revealed that the probe exhibits high selectivity and sensitivity towards Hg2+ in the presence of other common metal ions. A low detection limit of 23.4 nM was determined and a Job plot confirmed a 2:1 stoichiometry between QT and Hg2+. The potential utility of QT as a sensor for Hg2+ ions in human HeLa cells was determined by confocal fluorescence microscopy, and its suitability for use in the field with environmental samples was tested with Whatman filter paper strips.
- Full Text:
- Date Issued: 2022
- Authors: Musikavanhu, Brian , Muthusamy, Selvaraj , Zhu, Dongwei , Xue, Zhaoli , Yu, Qian , Chivumba, Choonzo N , Mack, John , Nyokong, Tebello , Wang, Shengjun , Zhao, Long
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230362 , vital:49771 , xlink:href="https://doi.org/10.1016/j.saa.2021.120338"
- Description: A new Schiff base probe (QT) consisting of 8-aminoquinoline (Q) and thiophene-2-carboxaldehyde (T) moieties has been synthesized. QT undergoes chelation-enhanced fluorescence quenching when exposed to Hg2+ due to coordination by the sulfur and nitrogen atoms of QT thus forming a facile “turn-off” sensor. The formation of the chelation complex was confirmed by UV–visible absorption and emission spectral measurements, 1H NMR titration and density functional theory calculations. These studies revealed that the probe exhibits high selectivity and sensitivity towards Hg2+ in the presence of other common metal ions. A low detection limit of 23.4 nM was determined and a Job plot confirmed a 2:1 stoichiometry between QT and Hg2+. The potential utility of QT as a sensor for Hg2+ ions in human HeLa cells was determined by confocal fluorescence microscopy, and its suitability for use in the field with environmental samples was tested with Whatman filter paper strips.
- Full Text:
- Date Issued: 2022
Borneol-triarylcorrole hybrids with chiral-optical response and anticancer behaviours
- Fu, Bo, Wang, Lin, Yu, Xiaoxiao, Fang, Xianying, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Liang, Xu, Xu, Haijun
- Authors: Fu, Bo , Wang, Lin , Yu, Xiaoxiao , Fang, Xianying , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu , Xu, Haijun
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185294 , vital:44362 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109699"
- Description: A series of four multifunctional A2B type H3corroles with meso-borneol substituents at the B position have been synthesized and characterized. A detailed analysis of the optical properties was carried out, and a comparison was made with theoretical calculations to identify the key trends in the structure-property relationships. The meso-borneol substituent couples with the corrole core leading to clear CD signals in the B band region. Enhanced anti-cancer properties are observed in vitro relative to (−)-borneol with cell inhibition rates of up to 94%.
- Full Text:
- Date Issued: 2021
- Authors: Fu, Bo , Wang, Lin , Yu, Xiaoxiao , Fang, Xianying , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu , Xu, Haijun
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185294 , vital:44362 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109699"
- Description: A series of four multifunctional A2B type H3corroles with meso-borneol substituents at the B position have been synthesized and characterized. A detailed analysis of the optical properties was carried out, and a comparison was made with theoretical calculations to identify the key trends in the structure-property relationships. The meso-borneol substituent couples with the corrole core leading to clear CD signals in the B band region. Enhanced anti-cancer properties are observed in vitro relative to (−)-borneol with cell inhibition rates of up to 94%.
- Full Text:
- Date Issued: 2021
A chiral hemiporphyrazine derivative
- Wu, Yanping, Gai, Lizhi, Xiao, Xuqiong, Lu, Hua, Li, Zhifang, Mack, John, Harris, Jessica, Nyokong, Tebello, Shen, Zhen
- Authors: Wu, Yanping , Gai, Lizhi , Xiao, Xuqiong , Lu, Hua , Li, Zhifang , Mack, John , Harris, Jessica , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240404 , vital:50831 , xlink:href="https://doi.org/10.1002/asia.201600754"
- Description: The synthesis of an optically active hemiporphyrazine with chiral binaphthyl substituents (1) is reported, providing the first example of the incorporation of an intrinsically chiral moiety into the macrocyclic core of a hemiporphyrazine analogue. A negative circular dichroism (CD) signal is observed in the 325–450 nm region of the CD spectrum of (S,S)-1, while mainly positive bands are observed in the 220–325 nm region. Mirror symmetry is observed across the entire wavelength range of the CD spectra of (R,R)-1 and (S,S)-1. An irreversible one-electron oxidation wave with an onset potential at 1.07 V is observed by cyclic voltammetry, along with a reversible one-electron reduction wave at −0.85 V. Density functional calculations reproduce the experimentally observed data and trends, and provide further insight into the nature of the electronic transitions.
- Full Text:
- Date Issued: 2016
- Authors: Wu, Yanping , Gai, Lizhi , Xiao, Xuqiong , Lu, Hua , Li, Zhifang , Mack, John , Harris, Jessica , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240404 , vital:50831 , xlink:href="https://doi.org/10.1002/asia.201600754"
- Description: The synthesis of an optically active hemiporphyrazine with chiral binaphthyl substituents (1) is reported, providing the first example of the incorporation of an intrinsically chiral moiety into the macrocyclic core of a hemiporphyrazine analogue. A negative circular dichroism (CD) signal is observed in the 325–450 nm region of the CD spectrum of (S,S)-1, while mainly positive bands are observed in the 220–325 nm region. Mirror symmetry is observed across the entire wavelength range of the CD spectra of (R,R)-1 and (S,S)-1. An irreversible one-electron oxidation wave with an onset potential at 1.07 V is observed by cyclic voltammetry, along with a reversible one-electron reduction wave at −0.85 V. Density functional calculations reproduce the experimentally observed data and trends, and provide further insight into the nature of the electronic transitions.
- Full Text:
- Date Issued: 2016
Porphyrin dimers with a bridging chiral amide-bonded benzo-moiety
- Liang, Xu, Qin, Mingfeng, Zhou, Lin, Liu, Tingting, Li, Minzhi, Mack, John, Ndebele, Nobuhle, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Qin, Mingfeng , Zhou, Lin , Liu, Tingting , Li, Minzhi , Mack, John , Ndebele, Nobuhle , Nyokong, Tebello , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233433 , vital:50090 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.02.043"
- Description: The facile synthesis and characterization of four porphyrin dimers which introduced stereomeric centers with chiral amide-bonded para- and meta-disubstituted benzo-moiety is reported. Trends in the electronic structures and optical and redox properties are analyzed through a comparison with theoretical calculations to explore the effect of positional isomerism of the bridging benzene rings.
- Full Text:
- Date Issued: 2018
- Authors: Liang, Xu , Qin, Mingfeng , Zhou, Lin , Liu, Tingting , Li, Minzhi , Mack, John , Ndebele, Nobuhle , Nyokong, Tebello , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233433 , vital:50090 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.02.043"
- Description: The facile synthesis and characterization of four porphyrin dimers which introduced stereomeric centers with chiral amide-bonded para- and meta-disubstituted benzo-moiety is reported. Trends in the electronic structures and optical and redox properties are analyzed through a comparison with theoretical calculations to explore the effect of positional isomerism of the bridging benzene rings.
- Full Text:
- Date Issued: 2018
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 and photophysical properties of covalent conjugates of aqua platinum (II) and octacarboxy-substituted zinc phthalocyanine
- Bulgakov, Roman A, Kuznetsova, Nina A, Dolotova, Olga V, Solovieva, Ludmila I, Mack, John, Chidawanyika, Wadzanai J U, Kaliya, Oleg L, Nyokong, Tebello
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
- Full Text:
- Date Issued: 2012
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
- Full Text:
- Date Issued: 2012
Effect of peripheral fused ring substitution on the optical spectroscopy and electronic structure of metal phthalocyanine complexes
- Chidawanyika, Wadzanai J U, Mack, John, Shimizu, Soji, Kobayashi, Nagao, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Date Issued: 2009
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Date Issued: 2009
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