Synthesis and photophysicochemical properties of BODIPY dye functionalized gold nanorods for use in antimicrobial photodynamic therapy
- Kubheka, Gugu, Uddin, Imran, Amuhaya, Edith, Mack, John, Nyokong, Tebello
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239897 , vital:50778 , xlink:href="https://doi.org/10.1142/S108842461650070X"
- Description: A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.
- Full Text:
- Date Issued: 2016
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239897 , vital:50778 , xlink:href="https://doi.org/10.1142/S108842461650070X"
- Description: A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.
- Full Text:
- Date Issued: 2016
Synthesis and Photophysical Investigation of Tetraazaporphyrin Substituted with Aggregation‐Induced Emission (AIE) Active Moieties
- Tasso, Thiago T, Furuyama, Taniyuki, Mack, John, Nyokong, Tebello, Kobayashi, Nagao
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015
Synthesis, characterization and photophysical properties of an acenaphthalene fused-ring-expanded NIR absorbing aza-BODIPY dye
- Majumdar, Poulomi, Mack, John, Nyokong, Tebello
- Authors: Majumdar, Poulomi , Mack, John , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189763 , vital:44929 , xlink:href="https://doi.org/10.1039/C5RA14916A"
- Description: The synthesis and characterization of an NIR absorbing acenaphthalene fused-ring-expanded aza-BODIPY dye are reported. In contrast with its naphtho-fused analogue, a stable complex is obtained when the corresponding phthalonitrile is used as the precursor. A comparison is made with the photophysical properties of 3,5-diphenyl-aza-dibenzoBODIPY.
- Full Text:
- Date Issued: 2015
- Authors: Majumdar, Poulomi , Mack, John , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189763 , vital:44929 , xlink:href="https://doi.org/10.1039/C5RA14916A"
- Description: The synthesis and characterization of an NIR absorbing acenaphthalene fused-ring-expanded aza-BODIPY dye are reported. In contrast with its naphtho-fused analogue, a stable complex is obtained when the corresponding phthalonitrile is used as the precursor. A comparison is made with the photophysical properties of 3,5-diphenyl-aza-dibenzoBODIPY.
- Full Text:
- Date Issued: 2015
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Liang, Xu, Xu, Li, Li, Minzhi, Mack, John, Stone, Justin, Nyokong, Tebello, Jiang, Yu, Kobayashi, Nagao, Zhu, Weihua
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
- Full Text:
- Date Issued: 2015
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
- Full Text:
- Date Issued: 2015
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
Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
- Okujima, Tetsuo, Mack, John, Nakamura, Jun, Kubheka, Gugu, Nyokong, Tebello, Zhu, Hua, Komobuchi, Naoki, Ono, Noboru, Yamada, Hiroko, Uno, Hidemitsu, Kobayashi, Nagao
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
Photophysical and optical limiting properties of a novel distyryl-BODIPY with fused crown ether moieties
- May, Aviwe K, Stone, Justin, Ngoy, Bokolombe P, Mack, John, Nyokong, Tebello, Kimura, Mutsumi, Kobayashi, Nagao
- Authors: May, Aviwe K , Stone, Justin , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello , Kimura, Mutsumi , Kobayashi, Nagao
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239621 , vital:50749 , xlink:href="https://doi.org/10.1142/S1088424617500869"
- Description: The synthesis and characterization of a crown-ether-substituted 3,5-distyrylBODIPY dye with a 4-dimethylaminophenyl group at the meso-position is reported. The optical limiting properties were investigated at 532 nm, and the dye was found to have enhanced reverse saturable absorption responses during z-scan measurements. Theoretical calculations suggest that this may be due to the large dipole moment that is introduced by the benzo-fused crown ether and 4-dimethylaminophenyl substituents.
- Full Text:
- Date Issued: 2017
- Authors: May, Aviwe K , Stone, Justin , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello , Kimura, Mutsumi , Kobayashi, Nagao
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239621 , vital:50749 , xlink:href="https://doi.org/10.1142/S1088424617500869"
- Description: The synthesis and characterization of a crown-ether-substituted 3,5-distyrylBODIPY dye with a 4-dimethylaminophenyl group at the meso-position is reported. The optical limiting properties were investigated at 532 nm, and the dye was found to have enhanced reverse saturable absorption responses during z-scan measurements. Theoretical calculations suggest that this may be due to the large dipole moment that is introduced by the benzo-fused crown ether and 4-dimethylaminophenyl substituents.
- Full Text:
- Date Issued: 2017
Push–pull type manganese (III) corroles
- Liang, Xu, Fang, Junjia, Li, Minzhi, Chen, Qiuyun, Mack, John, Molupe, Nthabeleng, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Fang, Junjia , Li, Minzhi , Chen, Qiuyun , Mack, John , Molupe, Nthabeleng , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189201 , vital:44826 , xlink:href="https://doi.org/10.1142/S1088424617500778"
- Description: The synthesis of three low symmetry A2B type Mn(III)triarylcorroles with meso-aryl substituents that provide push–pull electron-donating and -withdrawing properties is reported. An analysis of the structure-property relationships for the optical and redox properties has been carried out through a comparison with the results of theoretical calculations. The results demonstrate that A2B type Mn(III)triarylcorroles interact strongly with cell-free circulating tumor deoxyribonucleic acid (ctDNA) in solution, and that the interaction constants are enhanced when a stronger electron-donating substituent is introduced at the 10-position of the meso-triarylcorrole ligand.
- Full Text:
- Date Issued: 2017
- Authors: Liang, Xu , Fang, Junjia , Li, Minzhi , Chen, Qiuyun , Mack, John , Molupe, Nthabeleng , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189201 , vital:44826 , xlink:href="https://doi.org/10.1142/S1088424617500778"
- Description: The synthesis of three low symmetry A2B type Mn(III)triarylcorroles with meso-aryl substituents that provide push–pull electron-donating and -withdrawing properties is reported. An analysis of the structure-property relationships for the optical and redox properties has been carried out through a comparison with the results of theoretical calculations. The results demonstrate that A2B type Mn(III)triarylcorroles interact strongly with cell-free circulating tumor deoxyribonucleic acid (ctDNA) in solution, and that the interaction constants are enhanced when a stronger electron-donating substituent is introduced at the 10-position of the meso-triarylcorrole ligand.
- Full Text:
- Date Issued: 2017
Optically active BODIPYs
- Lu, Hua, Mack, John, Nyokong, Tebello, Kobayashi, Nagao, Shen, Zhen
- Authors: Lu, Hua , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240421 , vital:50833 , xlink:href="https://doi.org/10.1016/j.ccr.2016.03.015"
- Description: This review highlights and summarizes various optically active BODIPY molecules and describes the analysis of their circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, to provide a platform for the rational design of novel optically active BODIPY structures and the development of new chiroptical applications. Possible future research directions are also discussed.
- Full Text:
- Date Issued: 2016
- Authors: Lu, Hua , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240421 , vital:50833 , xlink:href="https://doi.org/10.1016/j.ccr.2016.03.015"
- Description: This review highlights and summarizes various optically active BODIPY molecules and describes the analysis of their circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, to provide a platform for the rational design of novel optically active BODIPY structures and the development of new chiroptical applications. Possible future research directions are also discussed.
- Full Text:
- Date Issued: 2016
Photophysical studies of 2, 6-dibrominated BODIPY dyes substituted with 4-benzyloxystyryl substituents
- Ngoy, Bokolombe Pitchou, Molupe, Nthabeleng, Harris, Jessica, Fomo, Gertrude, Mack, John, Nyokong, Tebello
- Authors: Ngoy, Bokolombe Pitchou , Molupe, Nthabeleng , Harris, Jessica , Fomo, Gertrude , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233068 , vital:50053 , xlink:href="https://doi.org/10.1142/S1088424617500420"
- Description: A series of novel 2,6-dibrominated BODIPY dyes with styryl groups at the 3,5-positions has been prepared, and their photophysical properties have been analyzed to assess their potential utility for use as photosensitizers in photodynamic therapy and in bioimaging.
- Full Text:
- Date Issued: 2017
- Authors: Ngoy, Bokolombe Pitchou , Molupe, Nthabeleng , Harris, Jessica , Fomo, Gertrude , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233068 , vital:50053 , xlink:href="https://doi.org/10.1142/S1088424617500420"
- Description: A series of novel 2,6-dibrominated BODIPY dyes with styryl groups at the 3,5-positions has been prepared, and their photophysical properties have been analyzed to assess their potential utility for use as photosensitizers in photodynamic therapy and in bioimaging.
- Full Text:
- Date Issued: 2017
Spectroscopic investigations and theoretical calculations of DABCO induced xanthene bridged self-assembled zinc (II) porphyrin dimer
- Xu, Li, Huang, Tingting, Liang, Xu, Mack, John, Harris, Jessica, Nyokong, Tebello, Li, Minzhi, Zhu, Weihua
- Authors: Xu, Li , Huang, Tingting , Liang, Xu , Mack, John , Harris, Jessica , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240732 , vital:50866 , xlink:href="https://doi.org/10.1142/S1088424616500231"
- Description: An in-depth study of the electronic structure of a 1,4-diazabicyclo[2.2.2]octane (DABCO) induced molecular self-assembled xanthene-bridged and amide-bonded porphyrin dimer is reported. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are used to identify trends in the optical spectroscopic properties. B3LYP geometry optimization predicts the formation of an almost perfectly eclipsed structure with respect to the two porphyrin rings with the analogous pyrrole nitrogens separated by 7.7–8.1 Å. The observed distinctive derivative-shaped band morphology of the pseudo-Faraday-A11 terms in the MCD spectra has been used to identify the main electronic Q and B-bands and to validate the TD-DFT calculations. The absence of a discernible splitting of the redox steps or a quenching of the fluorescence demonstrates that there is no significant exciton coupling between the two porphyrin rings.
- Full Text:
- Date Issued: 2016
- Authors: Xu, Li , Huang, Tingting , Liang, Xu , Mack, John , Harris, Jessica , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240732 , vital:50866 , xlink:href="https://doi.org/10.1142/S1088424616500231"
- Description: An in-depth study of the electronic structure of a 1,4-diazabicyclo[2.2.2]octane (DABCO) induced molecular self-assembled xanthene-bridged and amide-bonded porphyrin dimer is reported. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are used to identify trends in the optical spectroscopic properties. B3LYP geometry optimization predicts the formation of an almost perfectly eclipsed structure with respect to the two porphyrin rings with the analogous pyrrole nitrogens separated by 7.7–8.1 Å. The observed distinctive derivative-shaped band morphology of the pseudo-Faraday-A11 terms in the MCD spectra has been used to identify the main electronic Q and B-bands and to validate the TD-DFT calculations. The absence of a discernible splitting of the redox steps or a quenching of the fluorescence demonstrates that there is no significant exciton coupling between the two porphyrin rings.
- Full Text:
- Date Issued: 2016
Aggregation control of robust water-soluble zinc (II) phthalocyanine-based photosensitizers
- Ikeuchi, Takuro, Mack, John, Nyokong, Tebello, Kobayashi, Nagao, Kimura, Mutsumi
- Authors: Ikeuchi, Takuro , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Kimura, Mutsumi
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239709 , vital:50757 , xlink:href="https://doi.org/10.1021/acs.langmuir.6b03552"
- Description: A water-soluble zinc phthalocyanine (ZnPc) complex with four negatively charged electron-withdrawing sulfonic acid substituents at the nonperipheral positions (α-ZnTSPc) is found to have a high singlet oxygen (1O2) quantum yield and exhibits high photostability. The formation of aggregates is hindered and the highest occupied molecular orbital is significantly stabilized, making α-ZnTSPc potentially suitable for its use as a photosensitizer for photodynamic therapy and photoimmunotherapy. Atomic force microscopy (AFM) reveals that mixtures of the negatively charged α-ZnTSPc complex with a similar positively charged ZnPc were found to result in the self-assembly of one-dimensional accordion-like fibers. Supramolecular fibers can be formed in aqueous solutions through intermolecular electrostatic and donor–acceptor interactions between the two water-soluble ZnPcs.
- Full Text:
- Date Issued: 2016
- Authors: Ikeuchi, Takuro , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Kimura, Mutsumi
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239709 , vital:50757 , xlink:href="https://doi.org/10.1021/acs.langmuir.6b03552"
- Description: A water-soluble zinc phthalocyanine (ZnPc) complex with four negatively charged electron-withdrawing sulfonic acid substituents at the nonperipheral positions (α-ZnTSPc) is found to have a high singlet oxygen (1O2) quantum yield and exhibits high photostability. The formation of aggregates is hindered and the highest occupied molecular orbital is significantly stabilized, making α-ZnTSPc potentially suitable for its use as a photosensitizer for photodynamic therapy and photoimmunotherapy. Atomic force microscopy (AFM) reveals that mixtures of the negatively charged α-ZnTSPc complex with a similar positively charged ZnPc were found to result in the self-assembly of one-dimensional accordion-like fibers. Supramolecular fibers can be formed in aqueous solutions through intermolecular electrostatic and donor–acceptor interactions between the two water-soluble ZnPcs.
- Full Text:
- Date Issued: 2016
Efficient energy transfer in ethynyl bridged corrole–BODIPY dyads
- Yan, Yu, Wu, Fan, Qin, Jiawei, Xu, Haijun, Shi, Maohu, Zhou, Jingfeng, Mack, John, Fomo, Gertrude, Nyokong, Tebello, Shen, Zhen
- Authors: Yan, Yu , Wu, Fan , Qin, Jiawei , Xu, Haijun , Shi, Maohu , Zhou, Jingfeng , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240899 , vital:50883 , xlink:href="https://doi.org/10.1039/C6RA12271J"
- Description: A series of new corrole–BODIPY dyads bridged by ethynyl linker moieties have been synthesized in high yields and fully characterized. The direction of energy transfer upon electronic excitation has been explored, and was found to be dependent on the number of corrole rings and their connection position on the BODIPY core. Intense bands in the absorption spectrum cover most of the visible region, which is potentially advantageous for capturing solar energy. Studies on the excitation spectra and lifetimes suggest that the energy transfer efficiency between the BODIPY and corrole moieties reaches almost 85%, which appears to be efficient in the context of energy transfer within the singlet manifold.
- Full Text:
- Date Issued: 2016
- Authors: Yan, Yu , Wu, Fan , Qin, Jiawei , Xu, Haijun , Shi, Maohu , Zhou, Jingfeng , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240899 , vital:50883 , xlink:href="https://doi.org/10.1039/C6RA12271J"
- Description: A series of new corrole–BODIPY dyads bridged by ethynyl linker moieties have been synthesized in high yields and fully characterized. The direction of energy transfer upon electronic excitation has been explored, and was found to be dependent on the number of corrole rings and their connection position on the BODIPY core. Intense bands in the absorption spectrum cover most of the visible region, which is potentially advantageous for capturing solar energy. Studies on the excitation spectra and lifetimes suggest that the energy transfer efficiency between the BODIPY and corrole moieties reaches almost 85%, which appears to be efficient in the context of energy transfer within the singlet manifold.
- Full Text:
- Date Issued: 2016
Photophysical properties of tetraphenylporphyrinsubphthalocyanine conjugates
- Managa, Muthumuni, Mack, John, Remiro-Buenamañana, Sonia, Tshangana, Charmaine, Cammidge, Andrew N, Nyokong, Tebello
- Authors: Managa, Muthumuni , Mack, John , Remiro-Buenamañana, Sonia , Tshangana, Charmaine , Cammidge, Andrew N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240766 , vital:50869 , xlink:href="https://doi.org/10.1142/S1088424615500959"
- Description: Novel tetraphenylporphyrin-subphthalocyanine conjugates have been prepared and characterized. An analysis of their optical spectroscopy and electronic structures using fluorescence emission and magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations, demonstrates that the two chromophores do not interact to any significant extent.
- Full Text:
- Date Issued: 2016
- Authors: Managa, Muthumuni , Mack, John , Remiro-Buenamañana, Sonia , Tshangana, Charmaine , Cammidge, Andrew N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240766 , vital:50869 , xlink:href="https://doi.org/10.1142/S1088424615500959"
- Description: Novel tetraphenylporphyrin-subphthalocyanine conjugates have been prepared and characterized. An analysis of their optical spectroscopy and electronic structures using fluorescence emission and magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations, demonstrates that the two chromophores do not interact to any significant extent.
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- Date Issued: 2016
Singly and Doubly N-Confused Calix [4] phyrin Organoplatinum (II) Complexes as Near-IR Triplet Sensitizers
- Pushpanandan, Poornenth, Maurya, Yogesh Kumar, Omagari, Toshihiro, Hirosawa, Ryuji, Ishida, Masatoshi, Mori, Shigeki, Yasutake, Yuhsuke, Fukatsu, Susumu, Mack, John, Nyokong, Tebello, Furuta, Hiroyuki
- Authors: Pushpanandan, Poornenth , Maurya, Yogesh Kumar , Omagari, Toshihiro , Hirosawa, Ryuji , Ishida, Masatoshi , Mori, Shigeki , Yasutake, Yuhsuke , Fukatsu, Susumu , Mack, John , Nyokong, Tebello , Furuta, Hiroyuki
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233144 , vital:50061 , xlink:href="https://doi.org/10.1021/acs.inorgchem.7b02047"
- Description: Organoplatinum(II) complexes of calix[4]phyrin analogues, singly N-confused calix[4]phyrin (Pt-2), and doubly N-confused calix[4]phyrin (Pt-3), were synthesized and characterized. The explicit structures of these organoplatinum(II) complexes were elucidated by single-crystal X-ray diffraction and spectroscopic studies. The introduction of N-confused pyrrole rings to the parent calix[4]phyrin scaffold was found to have profound effects on the photophysical properties, such as the bathochromic shifts of both the absorption and phosphorescence maxima. The triplet excited state properties of these platinum complexes were analyzed by DFT calculations at the B3LYP level. The organoplatinum(II) complexes derived from the deformed scaffolds can serve as potent triplet sensitizers for singlet oxygen generation under aerobic conditions.
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- Date Issued: 2017
- Authors: Pushpanandan, Poornenth , Maurya, Yogesh Kumar , Omagari, Toshihiro , Hirosawa, Ryuji , Ishida, Masatoshi , Mori, Shigeki , Yasutake, Yuhsuke , Fukatsu, Susumu , Mack, John , Nyokong, Tebello , Furuta, Hiroyuki
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233144 , vital:50061 , xlink:href="https://doi.org/10.1021/acs.inorgchem.7b02047"
- Description: Organoplatinum(II) complexes of calix[4]phyrin analogues, singly N-confused calix[4]phyrin (Pt-2), and doubly N-confused calix[4]phyrin (Pt-3), were synthesized and characterized. The explicit structures of these organoplatinum(II) complexes were elucidated by single-crystal X-ray diffraction and spectroscopic studies. The introduction of N-confused pyrrole rings to the parent calix[4]phyrin scaffold was found to have profound effects on the photophysical properties, such as the bathochromic shifts of both the absorption and phosphorescence maxima. The triplet excited state properties of these platinum complexes were analyzed by DFT calculations at the B3LYP level. The organoplatinum(II) complexes derived from the deformed scaffolds can serve as potent triplet sensitizers for singlet oxygen generation under aerobic conditions.
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- Date Issued: 2017
MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine
- Mack, John, Mkhize, Scebi, Safonoya, Evgeniya A, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016
Chiral Modulation from Molecular to Macroscopic levels by synthetic chiral-amide-bonded porphyrin dimers
- Liang, Xu, Qin, Mingfeng, Zhang, Xiaomei, Mack, John, Soy, Rodah, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Qin, Mingfeng , Zhang, Xiaomei , Mack, John , Soy, Rodah , Nyokong, Tebello , Zhu, Weihua
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186802 , vital:44535 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107637"
- Description: Six different nanoarchitectures were constructed by a series of synthetic bio-inspired chiral porphyrin dimers through molecular self-assembly behaviour. A plausible mechanism of chiral expression from the molecular to the macroscopic levels was investigated through an analysis of the optical spectroscopy and theoretical calculations.
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- Date Issued: 2019
- Authors: Liang, Xu , Qin, Mingfeng , Zhang, Xiaomei , Mack, John , Soy, Rodah , Nyokong, Tebello , Zhu, Weihua
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186802 , vital:44535 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107637"
- Description: Six different nanoarchitectures were constructed by a series of synthetic bio-inspired chiral porphyrin dimers through molecular self-assembly behaviour. A plausible mechanism of chiral expression from the molecular to the macroscopic levels was investigated through an analysis of the optical spectroscopy and theoretical calculations.
- Full Text:
- Date Issued: 2019
Corrosion resistance of aluminum against acid activation: Impact of benzothiazole-substituted gallium phthalocyanine
- Nnaji, Nnaemeka, Nwaji, Njemuwa N, Mack, John, Nyokong, Tebello
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa N , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187545 , vital:44670 , xlink:href="https://doi.org/10.3390/molecules24010207"
- Description: This study describes the adsorption behavior of organic inhibitors at the aluminum-HCl solution interface and their corrosion inhibition performance. The organic inhibitors employed are: 4-(benzo [d]thiazol-2ylthio)phthalonitrile (BTThio) and tetrakis[(benzo[d]thiazol-2-yl-thio)phthalocyaninato]gallium(III) chloride (ClGaBTThioPc). The corrosion behavior of these inhibitors is investigated using electrochemical and computational techniques. Open circuit potential results reveal predominant cathodic character for the mechanism of aluminum corrosion inhibition by the inhibitors. Inhibition efficiency values from potentiodynamic polarization measurements increase from 46.9 to 70.8% for BTThio and 59.7 to 81.0% for ClGaBTThioPc within the concentration range of 2 to 10 µM. Scanning electron microscopy (SEM) measurements reveal protection of the metal surface from acid attack, in the presence of the inhibitors and energy dispersive X-ray (EDX) measurements show that the most probable way by which the inhibitors protect the metal surface would be by shielding it from the corrosion attacks of Cl− from the acid. Quantum chemical parameters corroborate well with experimental findings.
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- Date Issued: 2019
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa N , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187545 , vital:44670 , xlink:href="https://doi.org/10.3390/molecules24010207"
- Description: This study describes the adsorption behavior of organic inhibitors at the aluminum-HCl solution interface and their corrosion inhibition performance. The organic inhibitors employed are: 4-(benzo [d]thiazol-2ylthio)phthalonitrile (BTThio) and tetrakis[(benzo[d]thiazol-2-yl-thio)phthalocyaninato]gallium(III) chloride (ClGaBTThioPc). The corrosion behavior of these inhibitors is investigated using electrochemical and computational techniques. Open circuit potential results reveal predominant cathodic character for the mechanism of aluminum corrosion inhibition by the inhibitors. Inhibition efficiency values from potentiodynamic polarization measurements increase from 46.9 to 70.8% for BTThio and 59.7 to 81.0% for ClGaBTThioPc within the concentration range of 2 to 10 µM. Scanning electron microscopy (SEM) measurements reveal protection of the metal surface from acid attack, in the presence of the inhibitors and energy dispersive X-ray (EDX) measurements show that the most probable way by which the inhibitors protect the metal surface would be by shielding it from the corrosion attacks of Cl− from the acid. Quantum chemical parameters corroborate well with experimental findings.
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- Date Issued: 2019
NIR Absorbing AzaBODIPY Dyes for pH Sensing
- Kubheka, Gugu, Mack, John, Nyokong, Tebello, Zhen, Shen
- Authors: Kubheka, Gugu , Mack, John , Nyokong, Tebello , Zhen, Shen
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186668 , vital:44523 , xlink:href="https://doi.org/10.3390/molecules25163689"
- Description: Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, in CH2Cl2. The effect of substituent position on the photophysical and pH sensing properties was analyzed through a comparison of the optical properties with the results of time-dependent density functional theory (TD-DFT) calculations. Protonation of the dimethylamino nitrogen atoms eliminates the intramolecular charge transfer properties of these compounds, and this results in a marked blue-shift of the main absorption bands to 696 and 730 nm, respectively, in CH2Cl2, and a fluorescence “turn-on” effect in the NIR region. The pH dependence studies reveal that the pKa values of the non-protonated 2a and 2b molecules are ca. 6.9 (±0.05) and 7.3 (±0.05), respectively, while that of the monoprotonated species for both dyes is ca. 1.4 (±0.05) making them potentially suitable for use as colorimetric pH indicators under highly acidic conditions.
- Full Text:
- Date Issued: 2020
- Authors: Kubheka, Gugu , Mack, John , Nyokong, Tebello , Zhen, Shen
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186668 , vital:44523 , xlink:href="https://doi.org/10.3390/molecules25163689"
- Description: Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, in CH2Cl2. The effect of substituent position on the photophysical and pH sensing properties was analyzed through a comparison of the optical properties with the results of time-dependent density functional theory (TD-DFT) calculations. Protonation of the dimethylamino nitrogen atoms eliminates the intramolecular charge transfer properties of these compounds, and this results in a marked blue-shift of the main absorption bands to 696 and 730 nm, respectively, in CH2Cl2, and a fluorescence “turn-on” effect in the NIR region. The pH dependence studies reveal that the pKa values of the non-protonated 2a and 2b molecules are ca. 6.9 (±0.05) and 7.3 (±0.05), respectively, while that of the monoprotonated species for both dyes is ca. 1.4 (±0.05) making them potentially suitable for use as colorimetric pH indicators under highly acidic conditions.
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- Date Issued: 2020
A 3, 5-DistyrylBODIPY Dye Functionalized with Boronic Acid Groups for Direct Electrochemical Glucose Sensing
- Ndebele, Nobuhle, Mack, John, Nyokong, Tebello
- Authors: Ndebele, Nobuhle , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187556 , vital:44671 , xlink:href="https://doi.org/10.1002/elan.201800651"
- Description: The synthesis and characterization of a novel BODIPY dye functionalized with bis-boronic acid groups to enable direct glucose sensing through selective recognition of carbohydrates is reported. Styrylation with boronic acid groups at the 3,5-positions of the BODIPY core results in an extension of the π-conjugation system of the dye and in a red-shift of the main absorption band from 500 to 637 nm. The functionalized BODIPY dye was adsorbed on a glassy carbon electrode using the drop and dry method. Modified and bare electrodes were characterized using cyclic voltammetry and scanning electrochemical microscopy, while glucose detection was carried out by using differential pulse voltammetry and chronoamperometry. The detection limit was determined to be 1.42 μM. The dye was found to be selective and sensitive towards glucose, since likely interferences have only minor effects on the glucose detection.
- Full Text:
- Date Issued: 2019
- Authors: Ndebele, Nobuhle , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187556 , vital:44671 , xlink:href="https://doi.org/10.1002/elan.201800651"
- Description: The synthesis and characterization of a novel BODIPY dye functionalized with bis-boronic acid groups to enable direct glucose sensing through selective recognition of carbohydrates is reported. Styrylation with boronic acid groups at the 3,5-positions of the BODIPY core results in an extension of the π-conjugation system of the dye and in a red-shift of the main absorption band from 500 to 637 nm. The functionalized BODIPY dye was adsorbed on a glassy carbon electrode using the drop and dry method. Modified and bare electrodes were characterized using cyclic voltammetry and scanning electrochemical microscopy, while glucose detection was carried out by using differential pulse voltammetry and chronoamperometry. The detection limit was determined to be 1.42 μM. The dye was found to be selective and sensitive towards glucose, since likely interferences have only minor effects on the glucose detection.
- Full Text:
- Date Issued: 2019