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
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.
- Full Text:
- 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.
- Full Text:
- Date Issued: 2017
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
Synthetic analogues of the marine bisindole deoxytopsentin: potent selective inhibitors of MRSA pyruvate kinase
- Veale, Clinton G L, Zoraghi, Roya, Young, Ryan M, Morrison, James P, Pretheeban, Manoj, Lobb, Kevin A, Reiner, Neil E, Andersen, Raymond J, Davies-Coleman, Michael T
- Authors: Veale, Clinton G L , Zoraghi, Roya , Young, Ryan M , Morrison, James P , Pretheeban, Manoj , Lobb, Kevin A , Reiner, Neil E , Andersen, Raymond J , Davies-Coleman, Michael T
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/448045 , vital:74693 , xlink:href="https://doi.org/10.1021/np500755v"
- Description: As part of an ongoing study to elucidate the SAR of bisindole alkaloid inhibitors against the evolutionary conserved MRSA pyruvate kinase (PK), we present here the synthesis and biological activity of six dihalogenated analogues of the naturally occurring sponge metabolite deoxytopsentin, including the naturally occurring dibromodeoxytopsentin. The most active compounds displayed potent low nanomolar inhibitory activity against MRSA PK with concomitant significant selectivity for MRSA PK over human PK orthologues. Computational studies suggest that these potent MRSA PK inhibitors occupy a region of the small interface of the enzyme tetramer where amino acid sequence divergence from common human PK orthologues may contribute to the observed selectivity.
- Full Text:
- Date Issued: 2015
- Authors: Veale, Clinton G L , Zoraghi, Roya , Young, Ryan M , Morrison, James P , Pretheeban, Manoj , Lobb, Kevin A , Reiner, Neil E , Andersen, Raymond J , Davies-Coleman, Michael T
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/448045 , vital:74693 , xlink:href="https://doi.org/10.1021/np500755v"
- Description: As part of an ongoing study to elucidate the SAR of bisindole alkaloid inhibitors against the evolutionary conserved MRSA pyruvate kinase (PK), we present here the synthesis and biological activity of six dihalogenated analogues of the naturally occurring sponge metabolite deoxytopsentin, including the naturally occurring dibromodeoxytopsentin. The most active compounds displayed potent low nanomolar inhibitory activity against MRSA PK with concomitant significant selectivity for MRSA PK over human PK orthologues. Computational studies suggest that these potent MRSA PK inhibitors occupy a region of the small interface of the enzyme tetramer where amino acid sequence divergence from common human PK orthologues may contribute to the observed selectivity.
- Full Text:
- Date Issued: 2015
Enhanced Optical Limiting Behavior of an Indium Phthalocyanine–Single-Walled Carbon Nanotube Composite
- Sanusi, Kayode, Amuhaya, Edith K, Nyokong, Tebello
- Authors: Sanusi, Kayode , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193871 , vital:45401 , xlink:href="https://doi.org/10.1021/jp501469e "
- Description: The nonlinear optical behavior of 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (2) and its carbon nanotube composite in dimethylsulfoxide (DMSO) and dimethylformamide (DMF) solutions is described. The nonlinear third-order susceptibility and second-order hyperpolarizability values are also reported. A large nonlinear absorption that increased on covalent linking with single-walled carbon nanotubes (SWCNTs) was observed for the compound in DMSO. The nanosecond nonlinear absorption and the optical limiting behavior of this complex are shown to be dominated by a strong excited state absorption from a two-photon pumped state. The optical limiter using the new nanocomposite material (SWCNT-2) in the appropriate solvent showed a much lower threshold for optical limiting together with a much lower transmission at high fluences than previously reported nanocomposite limiters. The optical properties of the phthalocyanine and its conjugate were found to show high sensitivity toward the change of solvent matrix.
- Full Text:
- Date Issued: 2014
- Authors: Sanusi, Kayode , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193871 , vital:45401 , xlink:href="https://doi.org/10.1021/jp501469e "
- Description: The nonlinear optical behavior of 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (2) and its carbon nanotube composite in dimethylsulfoxide (DMSO) and dimethylformamide (DMF) solutions is described. The nonlinear third-order susceptibility and second-order hyperpolarizability values are also reported. A large nonlinear absorption that increased on covalent linking with single-walled carbon nanotubes (SWCNTs) was observed for the compound in DMSO. The nanosecond nonlinear absorption and the optical limiting behavior of this complex are shown to be dominated by a strong excited state absorption from a two-photon pumped state. The optical limiter using the new nanocomposite material (SWCNT-2) in the appropriate solvent showed a much lower threshold for optical limiting together with a much lower transmission at high fluences than previously reported nanocomposite limiters. The optical properties of the phthalocyanine and its conjugate were found to show high sensitivity toward the change of solvent matrix.
- Full Text:
- Date Issued: 2014
Introducing chemistry students to the “real world” of chemistry
- Brown, Michael E, Cosser, Ronald C, Davies-Coleman, Michael T, Kaye, Perry T, Klein, Rosalyn, Lamprecht, Emmanuel, Lobb, Kevin A, Nyokong, Tebello, Sewry, Joyce D, Tshentu, Zenixole R, Van der Zeyde, Tino, Watkins, Gareth M
- Authors: Brown, Michael E , Cosser, Ronald C , Davies-Coleman, Michael T , Kaye, Perry T , Klein, Rosalyn , Lamprecht, Emmanuel , Lobb, Kevin A , Nyokong, Tebello , Sewry, Joyce D , Tshentu, Zenixole R , Van der Zeyde, Tino , Watkins, Gareth M
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/449360 , vital:74814 , xlink:href="https://doi.org/10.1021/ed8001539"
- Description: A majority of chemistry graduates seek employment in a rapidly changing chemical industry. Our attempts to provide the graduates with skills in entrepreneurship and the ability to understand and communicate with their chemical engineering colleagues, in addition to their fundamental knowledge of chemistry, are described. This is done at second-year level with practical projects in which student teams formulate and prepare relatively simple chemical products for marketing, followed a year later by a more advanced study of the feasibility of producing and marketing a fine chemical on a commercial scale.
- Full Text:
- Date Issued: 2010
- Authors: Brown, Michael E , Cosser, Ronald C , Davies-Coleman, Michael T , Kaye, Perry T , Klein, Rosalyn , Lamprecht, Emmanuel , Lobb, Kevin A , Nyokong, Tebello , Sewry, Joyce D , Tshentu, Zenixole R , Van der Zeyde, Tino , Watkins, Gareth M
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/449360 , vital:74814 , xlink:href="https://doi.org/10.1021/ed8001539"
- Description: A majority of chemistry graduates seek employment in a rapidly changing chemical industry. Our attempts to provide the graduates with skills in entrepreneurship and the ability to understand and communicate with their chemical engineering colleagues, in addition to their fundamental knowledge of chemistry, are described. This is done at second-year level with practical projects in which student teams formulate and prepare relatively simple chemical products for marketing, followed a year later by a more advanced study of the feasibility of producing and marketing a fine chemical on a commercial scale.
- Full Text:
- Date Issued: 2010
Transformations of manool. Tri-and tetracyclic norditerpenoids with in vitro activity against plasmodium falciparum
- van Wyk, Albert W W, Lobb, Kevin A, Mino, Caira R, Hoppe, Heinrich C, Davies-Coleman, Michael T
- Authors: van Wyk, Albert W W , Lobb, Kevin A , Mino, Caira R , Hoppe, Heinrich C , Davies-Coleman, Michael T
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/450511 , vital:74956 , xlink:href="https://doi.org/10.1021/np0701071"
- Description: The known 17-norisopimar-15-ene-8‚,13‚-diol (5) and five new semisynthetic norditerpenoids, ethyl 17-norabiet-13-(15)-E-en-8‚-ol-16-oate (6), ethyl 17-norabiet-13(15)-Z-en-8‚-ol-16-oate (7), 17-norpimaran-13R-ethoxy-8,16-olactone(8), 17-norisopimarane-8‚,15-diol (9), and 17-norarabiet-13(15)-ene-8‚,16-diol (10), were prepared from manool (11).Standard spectroscopic data including X-ray crystal analysis were used to determine the structures of5-10. All fivecompounds exhibited in Vitroantiplasmodial activity against the malarial parasitePlasmodium falciparumat varyingÌgmL-1concentrations.
- Full Text:
- Date Issued: 2007
- Authors: van Wyk, Albert W W , Lobb, Kevin A , Mino, Caira R , Hoppe, Heinrich C , Davies-Coleman, Michael T
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/450511 , vital:74956 , xlink:href="https://doi.org/10.1021/np0701071"
- Description: The known 17-norisopimar-15-ene-8‚,13‚-diol (5) and five new semisynthetic norditerpenoids, ethyl 17-norabiet-13-(15)-E-en-8‚-ol-16-oate (6), ethyl 17-norabiet-13(15)-Z-en-8‚-ol-16-oate (7), 17-norpimaran-13R-ethoxy-8,16-olactone(8), 17-norisopimarane-8‚,15-diol (9), and 17-norarabiet-13(15)-ene-8‚,16-diol (10), were prepared from manool (11).Standard spectroscopic data including X-ray crystal analysis were used to determine the structures of5-10. All fivecompounds exhibited in Vitroantiplasmodial activity against the malarial parasitePlasmodium falciparumat varyingÌgmL-1concentrations.
- Full Text:
- Date Issued: 2007
Comparative Spectroscopic and Electrochemical Properties of Bis (octakis (dodecylthio) naphthalocyaninato) europium (III) and Bis (tetra-tert-butylnaphthalocyaninato) europium (III) Complexes
- Nyokong, Tebello, Furuya, Fumio, Kobayashi, Nagao, Du, Daming, Liu, Wei, Jiang, Jianzhuang
- Authors: Nyokong, Tebello , Furuya, Fumio , Kobayashi, Nagao , Du, Daming , Liu, Wei , Jiang, Jianzhuang
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293174 , vital:57062 , xlink:href="https://doi.org/10.1021/ic990483b"
- Description: Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(SC12H25)8]2, 1} and bis(tetra-tert-butyl-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(t-Bu)4]2, 2} have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3·H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV−visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2 → 2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = −0.28 V (for 2) and −0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = −0.61, −1.64, −1.97, and −2.42 V, and for 1 they were observed at E1/2 = −0.62, −1.60, −1.86, and −2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared.
- Full Text:
- Date Issued: 2000
- Authors: Nyokong, Tebello , Furuya, Fumio , Kobayashi, Nagao , Du, Daming , Liu, Wei , Jiang, Jianzhuang
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293174 , vital:57062 , xlink:href="https://doi.org/10.1021/ic990483b"
- Description: Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(SC12H25)8]2, 1} and bis(tetra-tert-butyl-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(t-Bu)4]2, 2} have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3·H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV−visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2 → 2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = −0.28 V (for 2) and −0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = −0.61, −1.64, −1.97, and −2.42 V, and for 1 they were observed at E1/2 = −0.62, −1.60, −1.86, and −2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared.
- Full Text:
- Date Issued: 2000
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