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Aza boron-pyridyl-isoindoline analogues

  • Authors: Zhang, Hui , Wu, Yanping , Fan, Minhui , Xiao, Xuqiong , Mack, John , Kubheka, Gugu , Nyokong, Tebello , Lu, Hua
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/232912 , vital:50037 , xlink:href="https://doi.org/10.1039/C7NJ00707H"
  • Description: Several aza boron-pyridyl-isoindoline analogues are synthesized through a facile and scale-up two step reaction using 1,2-naphthalenedicarbonitrile as a starting material. These analogues show broad envelopes of intense vibrational bands in the absorption spectra with moderate fluorescence quantum yields in solution and the solid-state. An analysis of the structure–property relationships is described based on X-ray crystallography, optical spectroscopy, and theoretical calculations.
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  • Date Issued: 2017

Azide-derivatized gold nanosphere “clicked” to indium and zinc phthalocyanines for improved nonlinear optical limiting

  • Authors: Bankole, Owolabi M , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188249 , vital:44738 , xlink:href="https://doi.org/10.1016/j.molstruc.2017.01.088"
  • Description: We report on the conjugation of azide-derivatized gold nanoparticles (AuNPs) to alkyne moieties of ZnPc and InPc via azide-alkyne Huisgen cycloaddition reaction to form phthalocyanines-AuNPs (MPc-AuNPs) conjugates. The detailed structural characterizations of the composites were in good agreement with the expected results. The nonlinear absorption coefficients and other nonlinear optical limiting parameters were almost two times larger for the conjugates compared to free phthalocyanines. We established direct relationship between improved photophysical characterizations and enhanced nonlinear effects of reverse saturable absorption mechanisms favoured by excited triplet absorption of the phthalocyanines in the presence of AuNPs. The combination of InPc with AuNPs resulted in the lowest limiting intensity value of 0.06 J/cm2, hence the best performance in terms of optical limiting.
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  • Date Issued: 2017

Characterization and physicochemical studies of the conjugates of graphene quantum dots with differently charged zinc phthalocyanines

  • Authors: Matshitse, Refilwe , Sekhosana, Kutloana E , Achadu, Ojodomo John , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/189227 , vital:44829 , xlink:href="https://doi.org/10.1080/00958972.2017.1387652"
  • Description: Unsubstituted zinc phthalocyanine (ZnPc), 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) and Zn tetrasulfo phthalocyanine (ZnTSPc) were non-covalently (electrostatic and/or π–π interaction) attached to graphene quantum dots (GQDs) to form GQDs-Pc nanoconjugates. Relative to Pcs alone, the presence of GQDs improved the triplet quantum yields with the following values: GQDs-ZnPc (0.73), GQDs-ZnTPPcQ (0.76) and GQDs-ZnTSPc (0.67). Respective Förster resonance energy transfer (FRET) efficiencies were calculated to be 0.81, 0.80 and 0.28. However, singlet oxygen generating abilities of the as-synthesized nanoconjugates were relatively low due to the screening effect of GQDs and quenching in water. This study shows that, the type of Pc, loading and solvent used are among the vital properties to consider when constructing GQD-nanoconjugate systems with optimal triplet quantum yield properties and investigation of their physicochemical properties.
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  • Date Issued: 2017

Characterization of conjugates of NaYF4

  • Authors: Watkins, Zane , Uddin, Imran , Britton, Jonathan , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/238132 , vital:50589 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.10.011"
  • Description: NaYF4:Er/Yb/Gd upconversion nanoparticles (UCNP) capped with amino groups were covalently attached to chloro aluminium tetrasulphonated phthalocyanine (ClAlTSPc) and chloro aluminium tetracarboxy phthalocyanine (ClAlTCPc). The conjugates were characterized using different techniques such as infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). There was a decrease in the intensity of fluorescence emission spectra of the UCNPs at 658 nm in the presence of the phthalocyanines. This decrease indicates an energy transfer between the donor UCNP and conjugated accepting phthalocyanine (Pc), due to Förster resonance energy transfer (FRET). FRET efficiencies of 18% and 21% for ClAlTSPc and ClAlTCPc, respectively, were obtained. Oxygen generation by ClAlTSPc following FRET was proved.
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  • Date Issued: 2017

Characterization of phthalocyanine functionalized quantum dots by dynamic light scattering, laser Doppler, and capillary electrophoresis

  • Authors: Ramírez-García, Gonzalo , Oluwole, David O , Nxele, Siphesihle Robin , d’Orlyé, Fanny , Nyokong, Tebello , Bedioui, Fethi , Varenne, Anne
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/238184 , vital:50595 , xlink:href="https://doi.org/10.1007/s00216-016-0120-x"
  • Description: In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy.
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  • Date Issued: 2017

Cu (III) triarylcorroles with asymmetric push–pull meso-substitutions

  • Authors: Liang, Xu , Niu, Yingjie , Zhang, Ojanchong , Mack, John , Yi, Xiaoyi , Hlatshwayo, Zweli , Li, Minzhi , Zhu, Weihua , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/232947 , vital:50040 , xlink:href="https://doi.org/10.1039/C7DT00716G"
  • Description: The synthesis of four low symmetry A2B type Cu (III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties is reported, along with their structural characterization by NMR spectroscopy and X-ray crystallography. An analysis of the structure–property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry, and spectroelectrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type Cu(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolution reactions (HERs) and that their reactivity can be modulated by changing the nature of the B-position meso-substituent.
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  • Date Issued: 2017

Effects of charge on the photophysicochemical properties of zinc phthalocyanine derivatives doped onto silica nanoparticles

  • Authors: Peteni, Siwaphiwe , Sekhosana, Kutloano E , Britton, Jonathan , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188159 , vital:44728 , xlink:href="https://doi.org/10.1016/j.poly.2017.09.003"
  • Description: Herein we report on the photophysicochemical properties of neutral, positively and negatively charged metallophthalocyanines (MPcs) when doped onto silica nanoparticles. The MPcs are: unsubstituted ZnPc (complex 1, neutral), Zn tetraaminophenoxy phthalocyanine (ZnTAPhPc, complex 2, neutral), tetrakis[4-(iodo-N-methylpyridinium)thio] phthalocyanine (ZnTMPyPc, complex 3, cationic), and Zn tetra sulfophenoxy phthalocyanine (ZnTSPhPc, complex 4, anionic). Following doping onto SiNPs, the triplet quantum yields increased for neutral complex 1 and positively charged complex 3. However, singlet oxygen quantum yields increased for positively charged 3 (in 3-SiNPs) and the negatively charge 4 (in 4-SiNPs) and not for complex 1 (in 1-SiNPs), compared to Pcs alone, due to the screening effect.
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  • Date Issued: 2017

Effects of covalent versus non-covalent interactions on the electrocatalytic behavior of tetracarboxyphenoxyphthalocyanine in the presence of multi-walled carbon nanotubes

  • Authors: Shumba, Munyaradzi S , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188271 , vital:44740 , xlink:href="https://doi.org/10.1080/00958972.2017.1303679"
  • Description: Tetracarboxyphenoxy phthalocyanine was covalently linked to multi-walled carbon nanotubes and the conjugate was used for modification of glassy carbon electrodes for the detection of hydrogen peroxide. The electrocatalytic behavior was examined by cyclic voltammetry, square wave voltammetry, and rotating disk electrode. The results show that covalent linking is attractive in terms of high detecting currents, low overpotential, and high catalytic rate constants. Very low detection limits were observed with CoTCPhPc-DAMN-MWCNT(linked)-GCE at 0.33 nM. The resulting catalytic rate constant was 1.1 × 103 M−1s−1.
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  • Date Issued: 2017

Effects of substituents on the electrocatalytic activity of cobalt phthalocyanines when conjugated to graphene quantum dots

  • Authors: Centane, Sixolile , Achadu, Ojodomo John , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188237 , vital:44737 , xlink:href="https://doi.org/10.1002/elan.201700252"
  • Description: We report on the π–π interactions between graphene quantum dots (GQDs) and the following cobalt phthalocyanine derivatives: cobalt monocarboxyphenoxy phthalocyanine (complex 1), cobalt tetracarboxyphenoxyphthalocyanine (complex 2), and cobalt tetraaminophenoxy phthalocyanine (complex 3). The conjugates (conj) with GQDs are represented as 1@GQDs(conj), 2@GQDs(conj) and 3@GQDs(conj), respectively. The resulting phthalocyanine/GQDs conjugates were adsorbed on containing a glassy carbon electrode (GCE) using the drop and dry method. We explore the electrochemical properties of phthalocyanines functionalized with both electron withdrawing groups and electron donating groups when non-covalently linked to the π-electron rich graphene quantum dots. GCE/3, GCE/2@GQDs(conj) and GCE/1@GQDs(conj) had the lowest limits of detection (LOD). Sequentially modified electrodes showed less favourable detection limits compared to the conjugates.
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  • Date Issued: 2017

Effects of symmetry and the number of positive charges on the photocatalytic activity of indium phthalocyanines when embedded in electrospun fibers

  • Authors: Chakona, Gamuchirai , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188304 , vital:44743 , xlink:href="https://doi.org/10.1016/j.ica.2016.12.025"
  • Description: Photooxidations of bisphenol A and 4-chlorophenol were carried out in this study using two asymmetric indium(III) phthalocyanines photosensitizers: the first consisting of one quaternized 4-pyridyloxyl and no other substituents (complex 1) and the second containing three quaternized 4-pyridylsulfanyl units and one aminophenoxy (complex 3). The asymmetry of complex 3 is additionally caused by the presence of two linking atoms (O and S). The symmetrically substituted indium(III) phthalocyanine containing four quaternized 4-pyridyloxyl units (complex 2) was also studied. The complexes were embedded in electrospun polystyrene fiber for heterogeneous photocatalytic transformation of 4-chlorophenol and bisphenol A. When immobilized on electrospun fibers, complexes 1, 2 and 3 gave singlet oxygen values of 0.31, 0.39 and 0.50 in water, respectively. Complex 3 showed the best photocatalytic behavior with observed rate constants of 2.8 × 10−3 min−1 for bisphenol A and 3.8 × 10−3 min−1 for 4-chlorophenol.
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  • Date Issued: 2017

Electrocatalytic application for gold nanoparticles decorated sulfur-nitrogen co-doped graphene oxide nanosheets and nanosized cobalt tetra aminophenoxy phthalocyanine conjugates

  • Authors: Shumba, Munyaradzi S , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188260 , vital:44739 , xlink:href="https://doi.org/10.1016/j.electacta.2017.03.154"
  • Description: Sulfur and nitrogen affinity for gold is utilized to self-assemble gold nanorods (AuNRs) on S, N doped or S/N co-doped graphene oxide nanosheets (SGONS/AuNRs, NGONS/AuNRs or SNGONS/AuNRs) for enhancement of the electrocatalytic activity of nanosized cobalt tetra aminophenoxy phthalocyanine (complex 1) towards hydrogen peroxide detection. Of the electrodes containing AuNRs, 1-SNGONS/AuNRs-GCE gave the lowest limits of detection (LOD) of 0.012 μM followed by 1-SGONS/AuNRs-GCE and 1-AuNRs-SNGONS(seq)-GCE both with LOD of 0.016 μM. This work shows that in the absence of GONS (when AuNRs are alone and in the presence of 1 in 1/AuNRs-GCE), unfavorable detection limits are obtained and that doping of GONS is important in improving LOD. 1-SNGONS/AuNRs-GCE showed concentration dependent mechanisms resulting in two adsorption Gibbs energies (ΔGo) of −18.55 kJ mol−1 and −17.35 kJ mol−1 at high and low concentrations, respectively.
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  • Date Issued: 2017

Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol

  • Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
  • Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
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  • Date Issued: 2017

Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine

  • Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/233032 , vital:50049 , xlink:href="https://doi.org/10.1002/elan.201700084"
  • Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
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  • Date Issued: 2017

Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine

  • Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/242763 , vital:51076 , xlink:href="https://doi.org/10.1002/elan.201700084"
  • Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
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  • Date Issued: 2017

Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine

  • Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
  • Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
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  • Date Issued: 2017

Enantioselective electrochemical carbon-chloride bond cleavage of hexachlorocyclohexanes (HCHs) catalyzed by Mn (III) Cl-phthalocyanine

  • Authors: Wen, Junxia , Yu, Baoqui , Huang, Tingting , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua , Liang, Xu
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/189252 , vital:44831 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.09.020"
  • Description: A lipophilic and electron-rich metallophthalocyanine Mn(III)Cl(α,α′-n-OC5H11)8Pc has been synthesized and characterized. A series of electrochemical experiments demonstrate that the Mn(III)Cl(α,α′-n-OC5H11)8Pc complex can be used as a catalyst for highly efficient carbon-chloride bond cleavage of environmental toxic hexachlorocyclohexanes (HCHs) through electrochemical catalysis, and that the increased catalytic efficiency is related to the enantiomeric carbon-chloride σ-bond of HCHs.
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  • Date Issued: 2017

Exploiting Click Chemistry for the Covalent Immobilization of Tetra (4-Propargyloxyphenoxy) Metallophthalocyanines onto Phenylazide-Grafted Gold Surfaces

  • Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
  • Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
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  • Date Issued: 2017

First example of nonlinear optical materials based on nanoconjugates of sandwich phthalocyanines with quantum dots

  • Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
  • Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
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  • Date Issued: 2017

Flexible Metal–Porphyrin Dimers (M= MnIIICl, CoII, NiII, CuII)

  • Authors: Li, Minzhi , Zhang, Qian , Xu, Li , Zhu, Weihua , Mack, John , May, Aviwe K , Nyokong, Tebello , Kobayashi, Nagao , Liang, Xu
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/239676 , vital:50754 , xlink:href="https://doi.org/10.1002/cplu.201600475"
  • Description: Four metalloporphyrin dimers linked by bridging amide-bonded xanthene moieties and that contain either MnIII, CoII, NiII, or CuII metal centers were synthesized. Various spectroscopic, electrochemical, and spectroelectrochemical methods were used to study trends in their properties. Their electronic structure and optical properties were analyzed through a comparison of the electronic absorption and magnetic circular dichroism (MCD) spectral data with the results of time-dependent (TD)-DFT calculations.
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  • Date Issued: 2017

Fluorescence behaviour of supramolecular hybrids containing graphene quantum dots and pyrene-derivatized phthalocyanines and porphyrins

  • Authors: Achadu, Ojodomo John , Managa, Muthumuni , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188953 , vital:44801 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.10.029"
  • Description: Novel pyrene-derivatized zinc and cobalt phthalocyanines (Pcs) and porphyrins (Ps) were immobilized on graphene quantum dots (GQDs) to form GQDs-Pcs and GQDs-Ps supramolecular hybrids via the π–π stacking interaction method. Spectroscopic evidence shows that the resultant hybrids were stable owing to the strong π–π stacking interaction between the GQDs and the respective Pcs and Ps, thus leading to the fabrication of interesting and functional supramolecular hybrids by taking advantage of the delocalized π electron systems of GQDs and the macrocycles. The conjugates showed increased fluorescence quantum yields for the Pcs/Ps, but decreased values for the GQDs in the conjugates. These novel hybrid materials could potentially be deployed for studies in both fundamental and applied perspectives due to the synergistic contributions resulting from the combination of their excellent electronic and optical properties.
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  • Date Issued: 2017
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