Improved Photophysical and Photochemical Properties of Thiopheneethoxy Substituted Metallophthalocyanines on Immobilization onto Gold‐speckled Silica Nanoparticles
- Authors: Dube, Edith , Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187699 , vital:44688 , xlink:href="https://doi.org/10.1111/php.12879"
- Description: This work reports on the synthesis of tetrakis-[(thiophineethoxy) phthalocyaninato] indium(II) chloride (3). The photophysical behavior of complex 3 was compared to that of the Zn derivative (tetrakis-[(thiophineethoxy) phthalocyaninato] zinc(II) (complex 2)). The compounds were interacted with gold-speckled silica (GSS) nanoparticles via Au–S self assembly to afford the conjugates (2–GSS and 3–GSS). The photophysicochemical behavior of the compounds and their conjugates were assessed. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet and singlet oxygen quantum yields in comparison with complexes 2 and 3 alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.
- Full Text:
- Date Issued: 2018
Effect of doping vs covalent linking of a low symmetry zinc phthalocyanine to silica nanoparticles on singlet oxygen production
- Authors: Peteni, Siwaphiwe , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187873 , vital:44705 , xlink:href="https://doi.org/10.1016/j.ica.2018.06.029"
- Description: Tris[(4-(pyridin-4-ylthio)-2-thio-4-methylthiazol-5-yl)acetic acid phthalocyaninato] zinc (II) (3) was covalently linked to and doped onto SiNPs. An increase in triplet quantum yields for 3-SiNPs (linked) with decreasing lifetimes was observed. For 3-SiNPs (doped) there was a decrease in both the triplet quantum yield and lifetimes when compared to 3 alone. There was an increase in singlet oxygen quantum yields for 3-SiNPs (linked) compared to 3 from 0.67 to 0.80, while there was a decrease for 3-SiNPs (doped) to 0.25.
- Full Text:
- Date Issued: 2018
Photo-induced resonance energy transfer and nonlinear optical response in ball-type phthalocyanine conjugated to semiconductor and graphene quantum dots
- Authors: Nwaji, Njemuwa , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187959 , vital:44713 , xlink:href="https://doi.org/10.1039/C7NJ05196D"
- Description: The synthesis of ball-type zinc and gallium phthalocyanines (complexes 2 and 3) and their covalent linkage to glutathione (GSH) and amine functionalized quantum dots QDs) are reported in this work. Furthermore, their photophysical, photo-induced resonance energy transfer and optical limiting responses were investigated. We observed a decrease in the fluorescence quantum yields with a corresponding increase in the triplet quantum yields of the nanoconjugates in comparison to the phthalocyanine complexes alone. The reverse saturable absorption was found to be dependent on the excited state absorption, and the observed limiting threshold ranged from 0.32 to 1.43 J cm−2. Enhanced triplet parameters and nonlinear optical performance were found when the complexes were covalently linked to semiconductor quantum dots compared to carbon based graphene quantum dots.
- Full Text:
- Date Issued: 2018
In-situ synthesis of gold nanoparticles on graphene quantum dots-phthalocyanine nanoplatforms: First description of the photophysical and surface enhanced Raman scattering behaviour
- Authors: Nwahara, Nnamdi , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187638 , vital:44682 , xlink:href="https://doi.org/10.1016/j.jphotochem.2018.04.011"
- Description: Owing to the need for new low-dimensional molecular assemblies with tailored electronic properties, the current study presents a facile approach for the synthesis and assembly of gold nanoparticles (AuNPs) onto functional graphene quantum dots (GQDs)-phthalocyanines (Pcs) arrays and the investigation of their photophysical and surface enhanced Raman scattering (SERS) properties. The GQDs were functionalized with L-glutathione (GSH) (to form GQDs@GSH) in order to assist coupling to the low symmetry Zn tris–(tert–butyl) mono carboxyphenoxy (propionic acid) phthalocyanine (complex 1) to form 1@GQDs. The affinity of gold (Au) to sulphur (S) was exploited for the assembly of the AuNPs onto 1@GQDs platform to form 1@GQDs-AuNPs. Transmission electron microscopic investigations confirmed the formation of monodispersed, spherical Pc/GQDs@GSH/AuNPs hybrids. The nanocomposite displayed high triplet quantum yields, which translated into high singlet oxygen quantum yield as high as 87%. Furthermore, the formed composites demonstrated strong surface enhanced Raman scattering (SERS) properties with an unprecedented intrinsic maximal enhancement factor of more than 30-fold. These nanostructures also retain more than 90% of their original SERS intensities after a week of storage, displaying superb stability under ambient conditions. These results highlight the remarkable potential of this composite as a unique Raman-based PDT dosimetric agent.
- Full Text:
- Date Issued: 2018
Glycosylated zinc phthalocyanine-gold nanoparticle conjugates for photodynamic therapy
- Authors: Dube, Edith , Oluwole, David O , Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234524 , vital:50205 , xlink:href="https://doi.org/10.1016/j.saa.2018.05.081"
- Description: In this work, we report on the synthesis of tris-[(2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4′,5′-d]pyran-5-yl)methoxy)-2-(4-benzo[d]thiazol-2-ylphenoxyphthalocyaninato] zinc(II) (complex 3) and its linkage to gold nanoparticles (AuNPs) of different shapes through S-Au/N-Au self-assembly. The conjugates of complex 3 (with both gold nanorods (AuNR) and nanospheres (AuNS)), displayed decreased fluorescence quantum yield with corresponding improved triplet and singlet quantum yields compared to complex 3 alone, however 3-AuNR showed improved properties than 3-AuNS. Complex 3 showed relatively low in vitro dark cytotoxicity against the epithelial breast cancer cells with cell survival ≥ 85% at concentration ≤ 160 μg/mL but afforded reduced photodynamic therapy activity which may be due to aggregation. 3-AuNR afforded superior PDT activity with more than 50% viable cells at concentration ≥ 40 μg/mL in comparison to 3-AuNS with more than 50% viable cells at concentration ≥ 80 μg/mL. The superior activity of 3-AuNR is attributed to the photothermal therapy effect since nanorods absorb more light at 680 nm than nanospheres.
- Full Text:
- Date Issued: 2018
The effect of the cobalt and manganese central metal ions on the nonlinear optical properties of tetra (4-propargyloxyphenoxy) phthalocyanines
- Authors: Mwanza, Daniel , Louzada, Marcel , Britton, Jonathan , Sekhosana, Kutloano E , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233357 , vital:50083 , xlink:href="https://doi.org/10.1039/C8NJ00748A"
- Description: The metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (Mn(OAc)TPrOPhOPc) tetra propargyloxyphenoxy phthalocyanines were evaluated for their potential as optical limiting materials. The effect of the substituents and the central metal ions on the nonlinear optical properties was evaluated. The metal-free phthalocyanine exhibited better nonlinear optical properties when compared to the cobalt and manganese complexes owing to the metal ions quenching the excited state due to their half-filled d-orbitals. The nonlinear absorption coefficient (βeff, ×10−5 m MW−1) followed the trend of H2TPrOPhOPc > CoTPrOPhOPc > Mn(OAc)TPrOPhOPc. The values βeff (×10−5 m MW−1) using 532 nm Nd:YAG (560 nm monochromatic Ekspla) laser sources were 23.5 > 14.3 > 9.20 (14.4). The second-order nonlinear coefficient obtained using density functional theory calculations, the theoretical hyper-Rayleigh scattering (βHRS, ×10−28 esu), showed the decreasing trend for H2TPrOPhOPc (2.28) > CoTPrOPhOPc (2.10) > Mn(OAc)TPrOPhOPc (1.86). The 4-(propargyloxy)phenoxy substituents enhanced the optical limiting properties of the synthesized phthalocyanines.
- Full Text:
- Date Issued: 2018
Novel nano-dyad of homoleptic sandwich-type phthalocyanines with nitrogen doped graphene quantum dots for nonlinear optics
- Authors: Oluwole, David O , Nwaji, Njemuwa , Nene, Lindokuhle C , Mokone, Lesedi , Dube, Edith , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233386 , vital:50086 , xlink:href="https://doi.org/10.1039/C8NJ01707G"
- Description: The syntheses of neodymium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (2), bis europium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (3), bis dysprosium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (4) and their conjugated analogues with nitrogen doped quantum dots (NGQDs) are reported herein. The optical nonlinearity of the sandwich-type phthalocyanine complexes and their conjugates with NGQDs were studied in dimethyl sulfoxide using the open aperture Z-scan technique at an excitation wavelength of 532 nm with a 10 ns pulse. The nonlinear absorption coefficient (βeff) value of the samples ranges from 15 cm GW−1 to 89.6 cm GW−1. Complex 4 and its conjugates afforded a strong optical limiting behaviour compared to the other samples. These fabricated complexes and their conjugates with NGQDs could serve as a plausible nonlinear optical (NLO) material due to their fascinating NLO properties.
- Full Text:
- Date Issued: 2018
One-pot synthesis of graphene quantum dots–phthalocyanines supramolecular hybrid and the investigation of their photophysical properties
- Authors: Fomo, Gertrude , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188126 , vital:44725 , xlink:href="https://doi.org/10.1007/s10853-017-1539-y"
- Description: The synthesis of graphene quantum dots (GQDs) using organic compounds as carbon sources via bottom-up approaches has been widely developed, whereas their hybrids with other materials have been previously achieved post-synthetically via multi-step procedures. A novel approach for the preparation of supramolecular hybrid conjugates of GQDs and phthalocyanines (Pcs) via an in situ one-step bottom-up route was employed in this study. The as-synthesized GQDs and their Pc conjugates were characterized using different spectroscopic techniques and their photophysicochemical properties evaluated. Notably, the singlet oxygen quantum yields of the Pcs in the presence of GQDs were found to be 0.51 and 0.74 for 1-GQDs and 2-GQDs, respectively, as compared to the Pcs alone (0.18 and 0.70 for complex 1 and 2, respectively). The increase in triplet quantum yield (ΦT) values is complemented by a decrease in fluorescence quantum yield (ΦF). ΦT value of 0.96 obtained for the complex 2 after conjugation with GQDs is better or higher than the value of 0.74 as reported in the literature when complex 2 was conjugated to semiconductor QDs. Hence, this novel approach resulted in the derivation of hybrid materials with potentials for various photophysicochemical applications such as photodynamic therapy and photocatalysis.
- Full Text:
- Date Issued: 2018
Low symmetric metallophthalocyanine modified electrode via click chemistry for simultaneous detection of heavy metals
- Authors: Fomo, Gertrude , Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187914 , vital:44709 , xlink:href="https://doi.org/10.1016/j.jelechem.2018.02.016"
- Description: Beside different methods and materials used to develop electrochemical sensors, the modification of the electrode using click reaction based on metallophthalocyanine (MPc) compounds are shown to improve the stability and sensitivity of the sensor. This work reported the development of electrochemical sensor for mercury (II), Lead (II), copper (II) and cadmium (II) ions detection based on the synthesized novel low symmetry alkyne terminated cobalt Phthalocyanine (CoPc) derivative. Differential pulse stripping voltammetry (DPSV) technique was employed for the first time in simultaneous determination of trace levels of the above metal ions using modified glassy carbon electrode (GCE) via click chemistry. Under the optimum experimental conditions, the anodic peak current is proportional to the concentrations of metal ions over a wide range of 0 to 0.1 mM with nanolevel detection limit of 81.94, 327.71, 55.87 and 347.06 nM and the sensitivity of 866.23 ± 5.48, 215.82 ± 2.16, 1979.48 ± 11.47 and 204.50 ± 1.10 μA/mM for Hg(II), Cu(II), Pb(II) and Cd(II), respectively. The selectivity of the clicked-CoPc modified GCE toward Hg(II), Cu(II), Pb(II), Cd(II) present no interference from these metals ions. The fabricated electrochemical sensor exhibited very good electrochemical properties such as good reproducibility, stability, reusability and is suitable for the detection of heavy metal ions in tap water in our laboratory.
- Full Text:
- Date Issued: 2018
The Primary Demonstration of Exciton Coupling Effects on Optical Limiting Properties of Blue Double-Decker Lanthanide Phthalocyanine Salts
- Authors: Sekhosana, Kutloano E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234614 , vital:50213 , xlink:href="https://doi.org/10.1002/slct.201800597"
- Description: In this manuscript, novel green and blue sandwich-type rare-earth phthalocyanines (LnPc2) are presented. This parent green LnPc2 complex is named bis-{2(3),9(10),16(17),23(24)-tetra(4-tert-buylphenoxy) phthalocyaninato} neodymium (III) (2) and modified into blue LnPc2 complexes (3), (4) and (5) based on hexadecyltrimethylammonium ion, mononeodymium(III) diacetate and monodysprosium(III) diacetate as counter ions, respectively. These stable blue lanthanide Pc salts are highly soluble in many organic and inorganic solvents. All complexes 2, 3, 4 and 5 were studied for optical limiting for the first time using Z-scan at nanosecond regime in the visible absorption spectral wavelength (532 nm). Our studies reveal the advantage of exciton coupling in blue sandwich-type rare-earth phthalocyanines over the π-radicals (characterized by blue valence at 485 nm) in the green counterpart which are in resonance with the 532 nm wavelength for optical limiting application. Large singlet ground state to excited state absorption cross section ratios were found, particularly for complex 5 in comparison to that of complex 2.
- Full Text:
- Date Issued: 2018
Effects of the carboxylic acid substituents on the photophysical and nonlinear optical properties of asymmetrical Zn (II) phthalocyanines–quantum dots conjugates
- Authors: Mgidlana, Sithi , Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187662 , vital:44684 , xlink:href="https://doi.org/10.1080/24701556.2018.1503684"
- Description: This work reports on three asymmetrical Zn(II) phthalocyanines, namely: zinc(II) 3–(4-phenoxy)propanoic acid) phthalocyanine(1), zinc(II) 3–(4-phenoxy carboxylic acid) phthalocyanine (2) and zinc(II) 3–(4–oxy)phenoxy)acetic acid phthalocyanine (3) when covalently linked to glutathione(GSH) capped CdTe/ZnSe and CdTe/ZnSe/ZnO quantum dots (QDs). Of the Pc complexes alone, 1 afforded the highest triplet quantum yield (ΦT) value of 0.67 with corresponding largest nonlinear absorption coefficient (βeff) value of 14.0 cm/GW compared to 2 and 3. The conjugates afforded improved triplet quantum yield and nonlinear optical behavior in comparison to the Pc complexes alone.
- Full Text:
- Date Issued: 2018
Photophysicochemical behaviour and antimicrobial properties of monocarboxy Mg (II) and Al (III) phthalocyanine-magnetite conjugates
- Authors: Idowu, Mopelola A I , Xego, Solami , Arslanoglu, Yasin , Mark, John , Antunes, Edith M , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188205 , vital:44734 , xlink:href="https://doi.org/10.1016/j.saa.2017.12.052"
- Description: Asymmetric Mg (II) or Al (III) phthalocyanine (containing a COOH group and 3-pyridylsulfanyl units) was conjugated via an amide bond to amino functionalized magnetic nanoparticle (AIMN) to form MgPc-AIMN or AlPc-AIMN conjugate, and characterized. The photophysicochemical behaviour of the phthalocyanine–AIMN conjugates was investigated and compared to the asymmetric Pcs and to the simple mixture of Pc with AIMNs without a chemical bond, (MPc-AIMN (mixed)). The directed covalent linkage of AIMNs to the asymmetrical metallopthalocyanines afforded improvements in the singlet oxygen (ФΔ) and triplet state quantum yield (ФT) as well as singlet oxygen lifetimes for the MPcs–AIMN-linked conjugates compared to MPc-AIMN (mixed) and MPcs alone. The asymmetric phthalocyanines and their conjugates showed effective antimicrobial activity against Escherichia coli bacteria under illumination.
- Full Text:
- Date Issued: 2018
Synthesis, photophysicochemical and photodynamic antimicrobial chemotherapy studies of indium pyridyl phthalocyanines: Charge versus bridging atom
- Authors: Sindelo, Azole , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187650 , vital:44683 , xlink:href="https://doi.org/10.1016/j.ica.2018.02.020"
- Description: 2(3), 9(10), 16(17), 23(24)-Octapyridylsulfanyl phthalocyaninato chloroindium(III) (complex 1a) and its quaternized derivative 2(3), 9(10), 16(17), 23(24)-octamethylpyridylsulfanyl phthalocyaninato chloroindium (III) (complex 1b) were synthesised. The triplet quantum yields were 0.53 and 0.48 while the singlet oxygen quantum yields were 0.46 and 0.33 in DMF for 1a and 1b, respectively. The photodynamic antimicrobial chemotherapy (PACT) activity of 1b (containing 8 positive charges) was compared to those of 9(10),16(17),23(24)-tri-N-methyl-4-pyridylsulfanyl-2(3)-(4-aminophenoxy) phthalocyaninato chloro indium(III) triiodide (2) (containing 3 positive charges) and 2-[4-(N-Methylpyridyloxy) phthalocyaninato] chloroindium (III) iodide (3) (containing 4 positive charges). Complex 1b gave log reductions of 4.21, 8.30 and 3.21 for Gram(−) E. coli, Gram(+) S. aureus and C. albicans, respectively. When comparing 1b, 2 and 3, the largest log reductions for E. coli were obtained for complex 3 containing four positive charges hence showing it is not always the charge that determines the PACT activity, but the bridging atom in the phthalocyanine plays a role.
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- Date Issued: 2018
Optimizing phthalocyanine based dye-sensitized solar cells: The role of reduced graphene oxide
- Authors: Chindeka, Francis , Mashazi, Philani N , Britton, Jonathan , Fomo, Gertrude , Oluwole, David O , Sindelo, Azole , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187770 , vital:44695 , xlink:href="https://doi.org/10.1016/j.synthmet.2018.10.021"
- Description: Dye-sensitized solar cells (DSSC) were fabricated by incorporating graphene materials as catalysts at the counter electrode. Platinum was also used as a catalyst for comparison purposes. Different phthalocyanines: hydroxyl indium tetracarboxyphenoxy phthalocyanine (1), chloro indium octacarboxy phthalocyanine (2) and dibenzoic acid silicon phthalocyanine (3) were used as dyes. Complex 3 gave the highest power conversion efficiency (η) of 3.19% when using nitrogen doped reduced graphene oxide nanosheets (NrGONS) as a catalyst at the counter electrode, and TiO2 containing rGONS at the anode. The value is close to 3.8% obtained when using Pt catalyst instead of NrGONS at the cathode, thus confirming that NrGONS is a promising candidate to replace the more expensive Pt. The study also shows that placing rGONS on both the anode and cathode improves efficiency.
- Full Text:
- Date Issued: 2018
Incorporation of metal free and Ga 5, 10, 15, 20-tetrakis (4-bromophenyl) porphyrin into Pluronic F127-folic acid micelles
- Authors: Managa, Muthumuni , Ngoy, Bucolome P , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233256 , vital:50073 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.09.045"
- Description: ClGa 5,10,15,20-Tetrakis (4-bromophenyl) porphyrinato (ClGaTBrPP) and its metal free derivative were successfully synthesized and incorporated into Pluronic F127 polymeric micelles that has been conjugated to folic acid (FA) to form ClGaTBrPP-F127-FA (or H2TBrPP-F127-FA). For comparison, ClGaTBrPP-F127 and H2TBrPP-F127 (without FA) were also formed. The singlet oxygen quantum yield for ClGaTBrPP-F127-FA was higher (ΦΔ = 0.44) than that of H2TBrPP-F127-FA (ΦΔ = 0.37), due to the heavy atom effect of Ga in the former which encourages intersystem crossing to the triplet state. The same applies to ClGaTBrPP-F127 (ΦΔ = 0.47) and H2TBrPP-F127 (ΦΔ = 0.41). Thus, ΦΔ values decreased in the presence of FA, but still high enough for practical application of the nanodrug system. The binding constants Kb were determined to be 1.08 × 104 M−1, 2.51 × 105 M−1, 1.52 × 103 and 2.68 × 103 for H2TBrPP+F127-FA, ClGaTBrPP+F127-FA, ClGaTBrPP-F127 and H2TBrPP-F127, respectively. The Kp values were determined in biphasic octanol and water system.
- Full Text:
- Date Issued: 2018
Physicochemical properties of water soluble unsymmetrical phthalocyanine-folic acid conjugates
- Authors: Matlou, Gauta G , Kobayashi, Nagao , Kimura, Mutsumi , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233240 , vital:50071 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.10.030"
- Description: This work reports on the successful chemical linkage of folic acid (FA) to Zn mono carboxyphenoxy phthalocyanine (1) and Zn mono carboxyphenoxy tri–(tert–butyl) phthalocyanine (2). The amide bond linkage of FA to phthalocyanine (Pc) is achieved for the first time through the FA-NH2 and Pc-COOH and confirmed using FTIR, MS, elemental analysis and NMR. The linked conjugates were found to be water soluble compared to the physical mixtures of FA and Pc, which allowed for studies of singlet oxygen in water. The Pc-FA linked conjugates (1-FA and 2-FA) were found to be singlet oxygen generators with the following singlet oxygen quantum yields: 1-FA = 0.61 and 2-FA = 0.47 in DMSO and 1-FA = 0.17 and 2-FA = 0.12 in water.
- Full Text:
- Date Issued: 2018
Photophysical studies of graphene quantum dots-Pyrene-derivatized porphyrins conjugates when encapsulated within Pluronic F127 micelles
- Authors: Managa, Muthumuni , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187971 , vital:44714 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.09.031"
- Description: Pyrene-derivatized H2, GaCl, and Zn porphyrins were immobilized on graphene quantum dots (GQDs) to form (GQDs-H2TPrP, GQDs-GaClTPrP, and GQDs-ZnTPrP) conjugates through the π-π stacking interaction method followed by encapsulating into Pluronic F127 micelles to form (GQDs-H2TPrP + F127, GQDs-GaClTPrP + F127, and GQDs-ZnTPrP + F127). Spectroscopic evidence shows that the resultant conjugates were stable due to the strong π-π stacking interaction between the GQDs and the porphyrins. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. GQDs-GaClTPrP + F127 showed highest values of the binding constant (Kb). The Stern-Volmer constant (Ksv) for GQDs-ZnTPrP + F127 were the highest compared to other porphyrins derivatives.
- Full Text:
- Date Issued: 2018
In-situ synthesis of gold nanoparticles on graphene quantum dots-phthalocyanine nanoplatforms: First description of the photophysical and surface enhanced Raman scattering behaviour
- Authors: Nwahara, Nnamdi , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188183 , vital:44730 , xlink:href="https://doi.org/10.1016/j.jphotochem.2018.04.011"
- Description: Owing to the need for new low-dimensional molecular assemblies with tailored electronic properties, the current study presents a facile approach for the synthesis and assembly of gold nanoparticles (AuNPs) onto functional graphene quantum dots (GQDs)-phthalocyanines (Pcs) arrays and the investigation of their photophysical and surface enhanced Raman scattering (SERS) properties. The GQDs were functionalized with L-glutathione (GSH) (to form GQDs@GSH) in order to assist coupling to the low symmetry Zn tris–(tert–butyl) mono carboxyphenoxy (propionic acid) phthalocyanine (complex 1) to form 1@GQDs. The affinity of gold (Au) to sulphur (S) was exploited for the assembly of the AuNPs onto 1@GQDs platform to form 1@GQDs-AuNPs. Transmission electron microscopic investigations confirmed the formation of monodispersed, spherical Pc/GQDs@GSH/AuNPs hybrids. The nanocomposite displayed high triplet quantum yields, which translated into high singlet oxygen quantum yield as high as 87%. Furthermore, the formed composites demonstrated strong surface enhanced Raman scattering (SERS) properties with an unprecedented intrinsic maximal enhancement factor of more than 30-fold. These nanostructures also retain more than 90% of their original SERS intensities after a week of storage, displaying superb stability under ambient conditions. These results highlight the remarkable potential of this composite as a unique Raman-based PDT dosimetric agent.
- Full Text:
- Date Issued: 2018
Optical nonlinearity of pentadecylphenoxyl substituted sandwich–type metallophthalocyanines in the presence of Ag–CdSeTe/ZnTeSe nanocrystals: Effects of conjugation and central metals
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187899 , vital:44708 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.01.009"
- Description: Novel pentadecylphenoxyl substituted homoleptic sandwich–type metallophthalocyanines: bis (complexes 2 and 4 containing Eu and Dy, respectively) and tris (complexes 3 and 5 containing Eu and Dy, respectively) 2,9,16,23–tetrakis–(3–pentadecylphenoxyl) phthalocyanines and cadmium based (Ag–CdSeTe/ZnTeSe) nanocrystals (NCs) were synthesized. The nonlinear optical (NLO) behavior of the metallophthalocyanines and their composites with NCs were investigated using the open aperture Z–scan technique at excitation wavelength of 532 nm with 10 ns pulse. All of the samples exhibited interesting NLO attributes: among all the sandwich–type complexes, complex 5 afforded the most efficient NLO features accounting for large nonlinear absorption coefficient (βeff) value of 3500 cm/GW and limiting threshold (Ilim) value of 0.43 J cm−2. Overall, the composites of the triple decker sandwich–type complexes with Ag–CdSeTe/ZnTeSe yielded the best NLO characteristics with 3 and 5 accounting for the largest βeff value of 5500 cm/GW and Ilim value of 0.09 J cm−2. The synthesized complexes and their composites with NCs could be viable and efficient NLO absorber due to their interesting NLO activities.
- Full Text:
- Date Issued: 2018
Singlet oxygen generating properties of different sizes of charged Graphene quantum dot Nanoconjugates with a positively charged Phthalocyanine
- Authors: Matshitse, Refilwe , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187614 , vital:44680 , xlink:href="https://doi.org/10.1007/s10895-018-2247-y"
- Description: Various sizes of graphene quantum dots (GQDs) denoted as GQD2, GQD6 and GQD10 (increasing in size) were non-covalently attached to 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) to form GQDs-ZnTPPcQ nanoconjugates. X-ray photoelectron spectroscopy (XPS) showed that increasing sizes of GQDs decreases the atomic concentrations of oxygen, which leads to blue shift in spectra of the GQDs. Relative to Pcs alone (0.03), the presence of GQDs improved the singlet oxygen quantum yields with the following values: GQD2-ZnTPPcQ (0.17), GQD6-ZnTPPcQ (0.27) and GQD10-ZnTPPcQ (0.11). GQD2-ZnTPPcQ nanoconjugate system had the most ZnTPPcQ loading, but did not generate the most singlet oxygen species due to aggregation. This study shows that, the quantity of oxygen, size and quality of GQDs as well as amount of Pc loading are amongst the vital properties to consider when constructing GQD-nanoconjugate systems with optimal singlet oxygen quantum yields.
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- Date Issued: 2018