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Effect of gold nanoparticle shape on the photophysicochemical properties of sulphur containing metallophthalocyanines

  • Authors: Dube, Edith , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187048 , vital:44559 , xlink:href="https://doi.org/10.1016/j.molstruc.2018.12.091"
  • Description: In this work tetrakise[(thiopheneethoxy) phthalocyaninato] zinc(II) (1), tetrakise[(thiopheneethoxy) phthalocyaninato] indium (II) chloride (2), tetrakis [(benzo [d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (3), and tetrakis [(benzo [d]thiazol-2-yl phenoxy)phthalocyaninato] indium (II) chloride (4) were linked to both gold nanospheres (AuNSs) and gold nanotriangles (AuNTs) via Au-S and Au-N (the latter for complexes 3 and 4 only) self assembly. The photophysicochemical behaviour of complexes and their conjugates were studied. The conjugates yielded improved triplet and singlet quantum yields, with nanospheres displaying better properties than nanotriangles. The conjugates with a benzothiazole phenoxy substituent also yielded better properties than their thiophene ethoxy counterpart. These conjugates especially those with a benzothiazole phenoxy substituent have potential as photosensitisers for photodynamic therapy applications.
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  • Date Issued: 2019

Effect of gold nanoparticles shape and size on the photophysicochemical behaviour of symmetric and asymmetric zinc phthalocyanines

  • Authors: Dube, Edith , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187569 , vital:44672 , xlink:href="https://doi.org/10.1016/j.jlumin.2018.09.063"
  • Description: Glutathione (GSH) capped Au nanotriangles (AuNTs–GSH) and nanospheres (AuNSs–GSH) are covalently linked to symmetric Zn phthalocyanine (ZnPc) substituted with phenoxy propanoic acid substituents only (complex 1) and two asymmetric ZnPc, each containing one phenoxy propanoic acid and three benzothiazole phenoxy moieties (complex 2), and one phenoxy propanoic acid and no other ligands (complex 3). The photophysicochemical behaviour of Pc complexes and their conjugates were studied. All conjugates displayed improved triplet and singlet oxygen quantum yields with decreases in fluorescence quantum yields compared to their respective Pc complexes. The conjugates of asymmetric complexes 2 and 3, afforded much higher triplet and singlet oxygen quantum yields compared to the symmetric complex 1, and could serve as good candidates for photodynamic therapy
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  • Date Issued: 2019

Effect of symmetry and metal nanoparticles on the photophysicochemical and photodynamic therapy properties of cinnamic acid zinc phthalocyanine

  • Authors: Matlou, Gauta G , Managa, Muthumuni , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187026 , vital:44557 , xlink:href="https://doi.org/10.1016/j.saa.2019.02.005"
  • Description: In this study, a novel asymmetric cinnamic acid zinc phthalocyanine (ZnPc, 1) containing three tert-butyl substituents is reported. The asymmetric ZnPc (1) is further linked to amino functionalized magnetic nanoparticles (AMNPs) (1-AMNPs) and to cysteine functionalized silver nanoparticles (cys-AgNPs) (1-cys-AgNPs) through an amide bond. 1-AMNPs and 1-cys-AgNPs improved the triplet and singlet oxygen quantum yields of complex 1, this was also observed with the previously reported 2-AMNPs when compared to 2 while 3-AMNPs yielded an unexpected decrease in triplet quantum yield as compared to 3. The silver nanoparticles (1-cys-AgNPs) had a better effect on improving the singlet oxygen quantum yield of complex 1 than the magnetic nanoparticles (1- AMNPs). The Pcs and conjugates recorded low cell cytotoxicity in the dark and high photocytotoxicity against MCF-7 cells in-vitro. MCF-7 cell viabilities of less than 50% were recorded at 80 μg/mL making the Pcs and conjugates under study potential candidates for use as photosensitizers in cancer therapy.
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  • Date Issued: 2019

Electrocatalytic activity of a push pull Co (II) phthalocyanine in the presence of graphitic carbon nitride quantum dots

  • Authors: Nxele, Siphesihle R , Oluwole, David O , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186746 , vital:44530 , xlink:href="https://doi.org/10.1016/j.electacta.2019.134978"
  • Description: This work reports for the first time on the use of a conjugate of graphitic carbon nitride quantum dots (gCNQDs) with a push-pull asymmetrical cobalt phthalocyanine (CoPc) for electrochemical sensing. The nanocomposite is immobilized on a glassy carbon electrode (GCE) surface for the use in l-cysteine electrocatalysis. The nanocomposites were characterized using techniques such as X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, UV-vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Raman spectroscopy and electrochemical methods. The nanocomposites were immobilized by the drop-dry method, sequentially or when premixed in solution. Good electrocatalytic oxidation of l-cysteine was observed, especially by the sequentially modified electrode surface, with the CoPc on top of gCNQDs. The sensitivity was determined as 3.5 μA.mM-1 and the limit of detection (LoD) as 101.3 μM for GCE-gCNQDs, 0.65 μA.mM-1 and 0.96 μM for GCE-CoPc, 23.41 μA.mM-1 and 0.41 μM for gCNQDs-CoPc (premixed) and 100.5 μA.mM-1 and 0.02 μM for gCNQDs-CoPc (sequential). The electrode surfaces also showed high stability by continuous cyclization.
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  • Date Issued: 2019

Electrocatalytic Activity of Asymmetrical Cobalt Phthalocyanines in the Presence of N Doped Graphene Quantum Dots: The Push-pull Effects of Substituents

  • Authors: Nkhahle, Reitumetse , Sekhosana, Kutloano E , Centane, Sixolile , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186904 , vital:44546 , xlink:href="https://doi.org/10.1002/elan.201800837"
  • Description: A series of Co phthalocyanine (CoPc) derivatives and their respective nitrogen doped graphene quantum dot conjugates were used as catalysts towards the electrooxidation of hydrazine. Using a glassy carbon electrode as a support for the electrocatalysts, through cyclic voltammetry and chronoamperometry, the effects of combining the CoPcs with the nitrogen doped graphene quantum dots (NGQDs) were studied. The general observations made were that the NGQDs improve the catalytic activity of the CoPcs in both the p-p stacked and covalently linked conjugates by increasing the sensitivities and lowering the limits of detection with values as low as 0.43 mM being recorded.
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  • Date Issued: 2019

Electrocatalytic activity of ethynylbenzyl phthalocyanines when linked to quantum dots via click chemistry: Towards efficient oxygen reduction reaction and H2O2 oxidation

  • Authors: Mpeta, Lekhetho S , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187037 , vital:44558 , xlink:href="https://doi.org/10.1016/j.jelechem.2019.03.064"
  • Description: This work describes the conjugation of Co, Mn and Fe tetra ethynyl benzyl phthalocyanines to CdTe/ZnS quantum dots via click chemistry. The synthesized conjugates were then immobilised on glassy carbon electrode and their electrocatalytic activity towards hydrogen peroxide oxidation and oxygen reduction investigated. CoPc (1)-QDs showed superior electrocatalytic behaviour towards hydrogen peroxide catalysis with sensitivity of 2.8 × 105 μA/mM and limit of detection of 0.023 μM. On the other hand, FePc(3)-QDs showed the best oxygen reduction activity involving a direct 4-electron mechanism.
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  • Date Issued: 2019

Evaluation of the photosensitizing properties of zinc and indium tetra cinnamic acid phthalocyanines linked to magnetic nanoparticles on human breast adenocarcinoma cells

  • Authors: Matlou, Gauta G , Oluwole, David O , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187582 , vital:44673 , xlink:href="https://doi.org/10.1016/j.jlumin.2018.09.054"
  • Description: This work reports on the synthesis, photophysico-chemical properties and photodynamic therapy activity of novel zinc (1) and indium (2) tetra substituted cinnamic acid phthalocyanine (Pc) complexes linked to amino functionalized magnetic nanoparticles (AMNPs) through an amide bond. Asymmetric ZnPc complex (3) showed better triplet and singlet oxygen quantum yields as compared to its symmetrical analogues (1 and 2). The AMNPs (1-AMNPs and 2-AMNPs) linked conjugates depicted increased triplet quantum yields in comparison to their unlinked Pcs, while 3-AMNPs showed a decrease compared to 3. The complexes showed increased in-vitro photo-cytotoxic effect against MCF-7 cells with an increase in drug concentration. At 80 µg/mL, 2 and 3, 2-AMNPs and 3-AMNPs with higher singlet oxygen quantum yields caused more cytotoxic effect on the cancer cells in the presence of light as compared to 1 and 1-AMNPs respectively.
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  • Date Issued: 2019

Fabrication of efficient nonlinear optical absorber using Zn phthalocyanine-semiconductor quantum dots conjugates

  • Authors: Mgidlana, Sithi , Oluwole, David O , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187496 , vital:44663 , xlink:href="https://doi.org/10.1016/j.poly.2018.11.024"
  • Description: In this paper, we report on the synthesis of Zn(II) phthalocyanine derivatives and their conjugates with core/shell and core/shell/shell semiconductor quantum dots (SQDs). Zn(II) mono amino-carboxyethylphenoxy phthalocyanine (1), Zn(II) mono 3-carboxyphenoxy-tris(pyridin-2-yloxy) phthalocyanine (2) and Zn(II) mono aminophenoxy-tris(benzothiazole) phthalocyanine (3) were synthesized. The photophysical and optical limiting properties of the phthalocyanine (Pc) complexes and their conjugates with SQDs were investigated in dimethyl sulfoxide. The optical limiting behaviour of the Pc complexes and their conjugates were measured by the open aperture Z-scan technique at laser excitation wavelength of 532 nm with 10 ns pulse. The conjugates outperformed the Pc complexes alone with the conjugates of 2-SQDs affording highest nonlinear absorption coefficient (βeff) value of ∼80 cm/GW and lowest limiting threshold (Ilim) value of ∼0.27 J·cm−2 as compared to other samples while complex 1 gave low βeff and high Ilim values of 42.2 cm/GW and 1.39 J·cm−2, respectively.
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  • Date Issued: 2019

Fluorescence “turn-ON” nanosensor for cyanide ion using supramolecular hybrid of graphene quantum dots and cobalt pyrene-derivatized phthalocyanine

  • Authors: Achadu, Ojodomo John , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187594 , vital:44674 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.08.038"
  • Description: A functional hybrid of graphene quantum dots (GQDs) and cobalt pyrene-derivatized phthalocyanine (CoPc) used as a sensitive nanoprobe for the recognition of cyanide ion (CN−) is described in this work. The fluorescence of GQDs was quenched upon non-covalent (π-π stacking) hybrid formation with CoPc via a possible energy transfer pathway. However, in the presence of CN−, the interaction between GQDs and CoPc was perturbed, such that the fluorescence of GQDs initially quenched by CoPc was found to be efficiently recovered in the presence of CN−. Amongst the molecules and anions tested to ascertain their effects on the fluorescence behaviour of the hybrid, only CN− ion induced the tunable “off-on” restoration of the fluorescence of GQDs, which demonstrates the selectivity of the hybrid towards CN−. The restored fluorescence signals of the GQDs were linearly modulated by different concentrations of CN− and were used for the quantitative assay of CN− with high sensitivity coupled with rapid detection time. The detection was in the linear range of 1.0–50.0 nM with limits of detection (LOD) of 0.5 nM. The analysis of spiked samples for the recovery of CN− further demonstrated the applicability of the hybrid for the satisfactory detection of the target analyte.
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  • Date Issued: 2019

Inhibition of aluminium corrosion using benzothiazole and its phthalocyanine derivative

  • Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa , Fomo, Gertrude , Mack, John , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186949 , vital:44550 , xlink:href="https://doi.org/10.1007/s12678-019-00538-1"
  • Description: Cyclic voltammetry and potentiodynamic polarization techniques were used to study the effects of 4-[4-(1,3-benzothiazol2yl)phenoxy] phthalonitrile (BT) and tetrakis[(benzo[d]thiazol-2ylphenoxy) phthalocyaninato] gallium(III)chloride (ClGaBTPc) as aluminium corrosion inhibitors in 1.0 M hydrochloric acid. The presence of the inhibitors in the concentration range of 2 to 10 μM was found to retard the aluminium corrosion process such that the inhibition efficiency was found to range from 28.2 to 76.1% for BT and from 71.5 to 82.7% for ClGaBTPc. The latter was a better inhibitor. Scanning electron microscopy and energy-dispersive X-ray measurements reveal effective metal surface protection by the inhibitors, most probably by shielding it from the corrosion attacks of Cl− from the acid. The calculated quantum chemical parameters agreed with experimental results.
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  • Date Issued: 2019

Investigation of novel substituted zinc and aluminium phthalocyanines for photodynamic therapy of epithelial breast cancer

  • Authors: Mohammed, Imadalulla , Oluwole, David O , Nemakal, Majunatha , Sannegowda, Lokesh K , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186824 , vital:44537 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107592"
  • Description: A series of phthalonitrile ligands were synthesized by nucleophilic substitution reaction using the hydroxyl or sulfanyl group precursors and the nitro moiety of the nitrophthalonitrile to yield corresponding oxy or sulfanyl bridged ligands. These ligands were subsequently subjected to cyclocondensation reaction with diamagnetic metal ions like zinc and aluminium to afford symmetrically substituted zinc and aluminium phthalocyanine (Pc) complexes and polymers. The ligands and Pc complexes were characterized by 1 H nuclear magnetic resonance, fourier transform infrared, ultraviolet visible and mass spectrometric techniques. Additionally, thermal gravimetric, and elemental analyzer were used for characterization of the Pc complexes. The photophysical and photochemical behaviour of the Pc complexes were investigated in dimethyl sulfoxide. Additionally, the complexes were tested against epithelial breast cancer cells for photodynamic therapy (PDT) effect. The substituted ZnPc complexes afforded higher singlet oxygen quantum yields as compared to the AlPc analogue. All the complexes showed innocuous invitro dark cytotoxicity and moderate PDT effect.
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  • Date Issued: 2019

Magnetic nanoparticle-indium phthalocyanine conjugate embedded in electrospun fiber for photodynamic antimicrobial chemotherapy and photodegradation of methyl red

  • Authors: Sindelo, Azole , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186857 , vital:44540 , xlink:href="https://doi.org/10.1016/j.heliyon.2019.e02352"
  • Description: ClIn(III) octacarboxy phthalocyanine (ClInOCPc) when alone or conjugated to magnetic nanoparticles (MNPClInOCPc) was employed for both photodynamic antimicrobial chemotherapy of an unknown water sample and Staphylococcus aureus, and for photo-degradation of methyl red (MR). The singlet oxygen quantum yields (ΦΔ) in water using ClInOCPc and MNP-ClInOCPc embedded in polyacrylonitrile (PAN) electrospun fibers were 0.36 and 0.22, respectively. When in solution, MNP-ClInOCPc gave 90.6% photoinactivation of microbes in a water sample from the stream and of ClInOCPc resulted in 84.8 % photoinactivation. When embedded to the polymer, there was 48.0% clearance for ClInOCPc and 63.7% clearance for MNP-ClInOCPc for the microbes in the water sample from the stream. For the photo-degradation of MR, the rate of degradation increased with decrease of the MR concentration with the MNP-ClInOCPc having the fastest rate.
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  • Date Issued: 2019

Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV−Vis−NIR Spectra of Phthalocyanines

  • Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
  • Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
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  • Date Issued: 2019

Morphological influence of deposition routes on lead sulfide thin films

  • Authors: Mlowe, Sixberth , Shombe, Ginena B , Akerman, Matthew P , Mubofu, Egid B , O'Brien, Paul , Mashazi, Philani N , Nyokong, Tebello , Revaprasadu, Neerish
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186780 , vital:44533 , xlink:href="https://doi.org/10.1016/j.ica.2019.119116"
  • Description: A distorted single crystal structure of bis(piperidinedithiocarbamato)lead(II) complex and its subsequent use to deposit thin films is reported. Two deposition routes namely, aerosol-assisted chemical vapour deposition (AACVD) and spin coating deposition have been employed to obtain anisotropic lead sulfide (PbS) nanostructures. The thin films displayed rod to cubic shaped crystals for AACVD, and a range of cubes, star and dendritic morphologies with variation of temperatures were displayed for spin coated films. Optical band gaps between 1.32 and 1.55 eV as controlled by the change in temperature were observed for thin films deposited by AACVD. Powder X-ray diffraction (P-XRD) studies show that the films formed are composed of cubic crystalline PbS. The X-ray photoelectron spectroscopy (XPS) was used to investigate the effect of activation temperatures (350, 400 and 450 °C) on the chemical composition and oxidation states of PbS samples.
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  • Date Issued: 2019

New type of metal-free and Zinc (II), In (III), Ga (III) phthalocyanines carrying biologically active substituents: Synthesis and photophysicochemical properties and photodynamic therapy activity

  • Authors: Sen, Pinar , Managa, Muthumuni , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186971 , vital:44552 , xlink:href="https://doi.org/10.1016/j.ica.2019.03.010"
  • Description: This study reports on novel phthalocyanines having benzimidazole units which are known to have biological properties. 4-(4-(5-chloro-1H-benzo[d]imidazol-2-yl) substituted metal-free, Zn(II), In(III) and Ga(III) phthalocyanines were synthesized, these newly synthesized molecules that were substituted by oxygen bridges were fully characterized. For the purpose of determining their potency for photodynamic therapy, the photophysicochemical properties were investigated in DMSO. The H2Pc (4) showed higher fluorescence quantum yield and fluorescence lifetime as compared to metallated phthalocyanines derivatives. However, the highest singlet oxygen (ΦΔ) and triplet state quantum yields (ΦT) values were obtained with the In(III)Pc (5).
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  • Date Issued: 2019

Nonlinear optical behavior of n-tuple decker phthalocyanines at the nanosecond regime

  • Authors: Sekhosana, Kutloana E , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/234603 , vital:50212 , xlink:href="https://doi.org/10.1039/C9RA01836K"
  • Description: The coordination system of rare-earth n-tuple decker phthalocyanines would be better suited with appropriate metal ions with the correct coordination number and the solvent system of the reaction, amongst other reasons, for the formation of n-tuple decker phthalocyanines. As a result, these complexes are very rare. In this manuscript, we present new n-tuple decker phthalocyanines in the form of double- (complex 2), quadruple- (complex 3a) and sextuple-decker phthalocyanines (complex 3b), all of which contain neodymium and cadmium metal ions. The primary focus is the investigation of the nonlinear optical (NLO) mechanisms responsible for the observed reverse saturable absorption. While the extension of the π-electron system has been found to enhance the nonlinear optical behavior of complexes 3a and 3b, a change in the NLO mechanisms has been observed, with complex 2 lacking the triplet state population, as revealed by a laser flash photolysis technique. It has also been established that the excited state absorption cross sections follow a clear order of magnitude for the complexes under investigation: σ23 (for 3b) > σ23 (for 3a) > σ1m (for 2). This trend evidences the effects of the extension of the π-electron system.
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  • Date Issued: 2019

Nonlinear optical properties of metal free and nickel binuclear phthalocyanines

  • Authors: Kabwe, Kapambwe P , Louzada, Marcel , Britton, Jonathan , Olomola,Temitope O , Nyokong, Tebello , Khene, Samson M
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186846 , vital:44539 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.05.003"
  • Description: This work employs the open and closed Z-scan aperture technique to comparatively study the nonlinear optical (NLO) properties of nickel and metal free 4-tert-butylphenoxy phthalocyanine, biphenyl bridged bis-4-tert-butylphenoxy phthalocyanine and naphthalene bridged bis-4-tert-butylphenoxy phthalocyanine. Density functional theory (DFT) calculations of dipolar and octupolar ( J=1 and J=3) contribution were determined theoretically from hyper-Rayleigh scattering (HRS) response ( HRS) values.
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  • Date Issued: 2019

Nonlinear optical responses of carbazole-substituted phthalocyanines conjugated to graphene quantum dots and in thin films

  • Authors: Majeed, Shereen A , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello , Makhseed, Saad
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186938 , vital:44549 , xlink:href="https://doi.org/10.1016/j.jlumin.2019.04.034"
  • Description: Three different phthalocyanine complexes substituted with carbazoles were conjugated to graphene quantum dots (GQDs) through π–π stacking. The morphologies, sizes, and crystallinities of the nanoconjugates were determined using Raman spectroscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The nonlinear optical (NLO) properties of the metallophthalocyanines alone and when conjugated to the GQD nanomaterial in different solvents, as well as after having been embedded in thin films, were studied. The effects of the different substituents and solvents on the NLO properties of the metallophthalocyanines were evaluated. Enhancements in the photophysical properties of the complexes upon conjugation with the nanomaterial were observed. Fluorescence quantum yields, fluorescence lifetimes, triplet quantum yields, and triplet lifetimes were measured for the complexes, and for their conjugates in DMSO.
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  • Date Issued: 2019

Optical limiting and femtosecond pump-probe transient absorbance properties of a 3, 5-distyrylBODIPY dye

  • Authors: Ngoy, Bokolombe P , May, Aviwe K , Mack, John , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186835 , vital:44538 , xlink:href="https://doi.org/10.3389/fchem.2019.00740"
  • Description: The optical limiting (OL) properties of a 3,5-di-p-benzyloxystyrylBODIPY dye with an p-acetamidophenyl moiety at the meso-position have been investigated by using the open-aperture Z-scan technique at 532 nm with 10 ns laser pulses. There is a ca. 140 nm red shift of the main spectral band to 644 nm relative to the corresponding BODIPY core dye, due to the incorporation of p-benzyloxystyryl groups at the 3,5-positions. As a result, there is relatively weak absorbance across most of the visible region under ambient light conditions. Analysis of the observed reverse saturable absorbance (RSA) profiles demonstrates that the dye is potentially suitable for use in optical limiting applications as has been reported previously for other 3,5-distyrylBODIPY dyes. Time-resolved transient absorption spectroscopy and kinetic studies with femtosecond and nanosecond scale laser pulses provide the first direct spectral evidence that excited state absorption (ESA) from the S1 state is responsible for the observed OL properties.
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  • Date Issued: 2019

Photo-physicochemical properties and in vitro photodynamic therapy activity of morpholine-substituted Zinc (II)-Phthalocyanines π-π stacked on biotinylated graphene quantum dots

  • Authors: Nene, Lindokuhle , Managa, Muthumuni , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186993 , vital:44554 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.03.002"
  • Description: Two morpholine-substituted Zn(II) phthalocyanines, complex 4 and the cationic 5, were synthesized and conjugated to graphene quantum dots (GQDs) and biotinylated GQDs (GQDs-biotin) by non-covalent π-π interactions. The GQDs-biotin are prepared as potential nanoparticle-based Pc delivery vector combined with a receptor-mediated transport system using biotin. The photo-physicochemical properties of the Pc complexes and their corresponding conjugates were studied. Upon conjugation, the fluorescence quantum yields decrease for 4 and 5, however, the triplet quantum yields were increased for the conjugates. All samples demonstrated singlet oxygen generation. For conjugated complexes, the singlet quantum yields decreased due to the screening effect in some cases. An increase in the photodynamic therapy activities upon quaternization was observed for the conjugates, with the cell viability decreasing from 66.2% to 51.2% after treatment for 4-GQDs and 5-GQDs, respectively. A relatively better performance was also observed for the cationic complex in combination with the biotin functionalized GQDs, 5-GQDs-biotin, where the cell viability was 34.9% after treatment. Moreover, the cellular uptake of 5-GQDs-biotin over 24 h was relatively higher compared to Pc complex alone and other PcsGQDs conjugates.
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  • Date Issued: 2019
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