Modulation of the optical properties of chiral porphyrin dimers by introducing bridged chiral amide-bonds
- Authors: Qin, Mingfeng , Zhang, Zhen , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190815 , vital:45031 , xlink:href="https://doi.org/10.1142/S1088424620500492"
- Description: The d/l-enantiomers of a series of three Zn(II)tetraarylporphyrin dimers were synthesized and isolated by incorporating a bridging amide-bonded xanthene moiety at the para-position of one of the meso-aryl rings. The electronic structures and optical properties were modulated by incorporating chiral amino acid moieties into the amide-bonding moieties of the xanthene bridge that contain methyl, tolyl and 2-methylindole substituents. A cofacial dimer was formed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulting in a significant red shift of the B band, due to a relative destabilization of the HOMO, which has large MO coefficients on the pyrrole nitrogens. The sign sequences observed in the B band region of the CD spectra due to the presence of the chiral amino acid moieties were modified due to this change in geometry. Significant CD intensity is also observed in the B band region of the CD spectra of anion radical species during in situ spectroelectrochemical measurements.
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- Date Issued: 2021
Push-pull type Co (III) corroles
- Authors: Niu, Yingjie , Zhu, Weihua , Mack, John , Dubazana, Nadine , Nyokong, Tebello , Fu, Bo , Xu, Haijun , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190826 , vital:45032 , xlink:href="https://doi.org/10.1142/S1088424621500279"
- Description: The rational design and preparation of three A2B type Co(III)triarylcorroles with push- and pull-substituents are reported. The structure-property relationships were identified by comparing their optically spectroscopic and electrochemical properties to trends predicted in DFT and TD-DFT calculations. The results demonstrate that the Co(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolutions (HERs) and oxygen reductions (ORRs), and that their reactivity can be modulated by changing the meso-B-substituent of the Co(III)Corroles.
- Full Text:
- Date Issued: 2021
Turn-on detection of cysteine by a donor-acceptor type quinoline fluorophore: Exploring the sensing strategy and performance in bioimaging
- Authors: Muthusamy, Selvaraj , Zhao, Long , Rajalakshmi, Kanagaraj , Zhu, Dongwei , Soy, Rodah , Mack, John , Nyokong, Tebello , Wang, Shengjun , Lee, Kang-Bong , Zhu, Weihua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185644 , vital:44406 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109556"
- Description: Tracking the biothiol cysteine (Cys) in living systems is a significant responsibility to balance the redox environment and oxidative stress. A quinoline-7-nitro-1,2,3-benzoxadiazole (Q-NBD) fluorophore has been synthesized and characterized towards examination of Cys. The probe forms a quinoline-substituted phenol (Q-Ph-OH) after thiolysis of the NBD ether bond, leading to an increase of fluorescence at green channel. The turn-on sensing mechanism originates from the change in intramolecular charge transfer (ICT-OFF) along with an aggregation-induced emission (AIE) as suggested by spectroscopy measurements in solutions, time-dependent density-functional theory (TD-DFT) calculations and 1H NMR titration examination. Importantly, Q-NBD exhibited great sensitivity with a low limit of detection value of 89.5 nM and remarkable selectivity in various biothiols towards Cys. The sensor probe was successfully used for detecting both endogenous and exogenous Cys in PC3 living cells and spiked Cys in human urine samples.
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- Date Issued: 2021