Analytical Detection and Electrocatalysis of Paracetamol in Aqueous Media Using Rare‐Earth Double‐Decker Phthalocyaninato Chelates as Electrochemically Active Materials
- Authors: Sekhosana, Kutloana E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190840 , vital:45033 , xlink:href="https://doi.org/10.1002/slct.202002268"
- Description: Paracetamol (PA), being an analgesic and antipyretic medicine, can cause fatal hepatotoxicity and nephrotoxicity when overdosed. It is therefore important to develop electrochemical sensors that can monitor and quantify it in aquatic environments. In this study, rare-earth sandwich-type phthalocyaninato chelates based on neodymium (1 a) and samarium (1 b) were employed as electrocatalysts to modify glassy carbon electrodes (GCE) for the first time. It was found that 1 a-modified GCE (herein referred to as 1 a-GCE) is less conductive than 1 b-modified counterpart (1 b-GCE). A larger rate constant was also obtained for 1 b-GCE. It was established that a faster oxidation rate efficiency was responsible for lower limit of detection value obtained for 1 b-GCE as compared to 1 a-GCE.
- Full Text:
- Date Issued: 2020
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.
- Full Text:
- Date Issued: 2019
Electrocatalytic activity of a push-pull phthalocyanine in the presence of reduced and amino functionalized graphene quantum dots towards the electrooxidation of hydrazine
- Authors: Centane, Sixolile , Sekhosana, Kutloana E , Matshitse, Refilwe , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233456 , vital:50092 , xlink:href="https://doi.org/10.1016/j.jelechem.2018.05.005"
- Description: We report on the electrochemical behaviour of reduced graphene quantum dots (rGQDs) compared to amino functionalized graphene quantum dots (NH2GQDs). Reduction of the GQDs entails the elimination of the excessive carboxyl and hydrogen groups on the GQDs surface, thereby reducing the energy band gap. The energy band gap of graphene is directly proportional to the available oxygen atoms. The two GQD types were conjugated to a novel cobalt phthalocyanine (cobalt tris-(tert-butyl phenoxy)-mono-carboxyphenoxy phthalocyanine, CoPc) via covalent and nom-covalent interactions. The resulting conjugates were tested towards the electrooxidation of hydrazine. The conjugates are represented as rGQDs(π)CoPc, NH2(π)CoPc, rGQDs@CoPc and NH2GQDs@CoPc. The resulting conjugates were adsorbed onto a glassy carbon electrode using the drop and dry method. The lowest limit of detection (LOD) was obtained for rGQDs(π)CoPc.
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- Date Issued: 2018
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
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.
- Full Text:
- Date Issued: 2017
Nonlinear optical behavior of neodymium mono-and bi-nuclear phthalocyanines linked to zinc oxide nanoparticles and incorporated into poly acrylic acid
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188766 , vital:44783 , xlink:href="https://doi.org/10.1016/j.poly.2015.12.045"
- Description: Syntheses of bis{23-(3,4-di-yloxybenzoic acid)-(2(3), 9(10), 16(17), 23(24))-(hexakis-pyridin-3-yloxy phthalocyaninato)} dineodymium (III) acetate (3) and 2(3), 9(10), 16(17), 23(24)-(tetrapyridin-3-yloxy phthalocyaninato) neodymium (III) acetate (4) as well as their conjugates with ZnO nanoparticles (conjugates 6, 7 and 8) are presented. Thin films of conjugate 6 (where complex 3 is linked to ZnO nanoparticles via an amide bond) gave the best third-order susceptibility (5.89 × 10−8 esu), second-order hyperpolarizability (2.53 × 10−25 esu) and the lowest limiting threshold values (0.12 J cm−2). The nonlinear behavior is enhanced in solid state when compared to solution.
- Full Text:
- Date Issued: 2016
The optical limiting of blue and green ytterbium double-decker phthalocyanines in solution and in poly (acrylic acid) as thin films
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188585 , vital:44767 , xlink:href="https://doi.org/10.1016/j.ica.2016.05.026"
- Description: Bis{1(4), 8(11), 15(18), 22(25)-tetra(4-tert-butylphenoxy)phthalocyaninato} ytterbium(III) (2a) (the green form) was synthesized and reduced to form 2b (the blue form). Nonlinear optical parameters for complex 2 in green and blue forms were determined using the Z-scan technique and the values of third-order imaginary susceptibility (Im[χ(3)]) and second-order hyperpolarizability (γ) of the order of 10−9 (for 2b) and 10−27 esu, respectively, were obtained in solution. In poly(acrylic acid) as a thin film, complex 2a showed extremely high Im[χ(3)] and γ values of the order 10−8 and 10−25 respectively. A low optical limiting threshold value of 0.075 J cm−2 was obtained for the thin film 2a.
- Full Text:
- Date Issued: 2016
Nanosecond nonlinear optical limiting properties of new trinuclear lanthanide phthalocyanines in solution and as thin films
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189752 , vital:44928 , xlink:href="https://doi.org/10.1016/j.poly.2014.08.047"
- Description: 2,4,6-Tris[3-thio-9,10,16,17,23,24-hexa(4-tertbutylphenoxy) phthalocyaninato ytterbium (III) chloride]-s-triazin (3) and its lutetium counterpart (4) were synthesized. The nonlinear optical behavior of 3 and 4 were characterized in solution and when embedded in polymer as thin films. Thin films of complexes 3 and 4 in poly(bisphenol A carbonate) showed improved nonlinear optical properties when compared to solution. Complex 3 showed a lower threshold for optical limiting intensity (Ilim) than complex 4, and for phthalocyanines in general. Ilim values were even lower in films compared to solutions.
- Full Text:
- Date Issued: 2015
Synthesis, photophysical and nonlinear optical behavior of neodymium based trisphthalocyanine
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith K , Khene, Samson M , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241412 , vital:50937 , xlink:href="https://doi.org/10.1016/j.ica.2014.11.029"
- Description: Tris-{1(4),8(11),15(18),22(25)-tetra(4-tertbutylphenoxy) phthalocyaninato} dineodymium (III) was synthesised and its nonlinear optical and fluorescence behavior was studied. Low fluorescence quantum yield (ФF = 0.03) was obtained with a fluorescence lifetime τF = 4.31 ns for this complex. Nonlinear optical parameters for the complex were determined using the Z-scan technique and the values of Im[χ(3)] and γ were of the order of 10−10 and 10−28 esu, respectively. Square wave voltammetry revealed three reduction and two oxidation couples for the complex.
- Full Text:
- Date Issued: 2015
The nonlinear absorption in new lanthanide double decker pyridine-based phthalocyanines in solution and thin films
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189307 , vital:44836 , xlink:href="https://doi.org/10.1016/j.optmat.2015.05.022"
- Description: The optical behavior of bis-{2(3), 9(10), 16(17), 23(24)-(tetrapyridin-4-yloxy phthalocyaninato)} lanthanum (III) (2) and its ytterbium (3) counterpart in dimethyl sulfoxide are presented and compared to bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-4-yloxy phthalocyaninato)} ytterbium (III) (4). We report on the third-order susceptibility, second-order hyperpolarizability and the limiting threshold values. The nonlinear optical limiting threshold values of complexes 2, 3 and 4 showed improvement in the solid state (thin films), with complex 4 giving the best value at 0.033 J cm−2.
- Full Text:
- Date Issued: 2015
Synthesis and characterization of quantum dots designed for biomedical use
- Authors: Kuzyniak, Weronika , Adegoke, Oluwasesan , Sekhosana, Kutloana E , D'Souza, Sarah , Tshangana, Sesethu Charmaine , Hoffmann, Björn , Ermilov, Eugeny A , Nyokong, Tebello , Höpfner, Michael
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241516 , vital:50946 , xlink:href="https://doi.org/10.1016/j.ijpharm.2014.03.037"
- Description: Semiconductor quantum dots (QDs) have become promising nanoparticles for a wide variety of biomedical applications. However, the major drawback of QDs is their potential toxicity. Here, we determined possible cytotoxic effects of a set of QDs by systematic photophysical evaluation in vitro as well as in vivo. QDs were synthesized by the hydrothermal aqueous route with sizes in the range of 2.0–3.5 nm. Cytotoxic effects of QDs were studied in the human pancreatic carcinoid cell line BON. Cadmium telluride QDs with or without zinc sulfide shell and coated with 3-mercaptopropionic acid (MPA) were highly cytotoxic even at nanomolar concentrations. Capping with L-glutathione (GSH) or thioglycolic acid (TGA) reduced the cytotoxicity of cadmium telluride QDs and cadmium selenide QDs. Determination of the toxicity of QDs revealed IC50 values in the micromolar range. In vivo studies showed good tolerability of CdSe QDs with ZnS shell and GSH capping. We could demonstrate that QDs with ZnS shell and GSH capping exhibit low toxicity and good tolerability in cell models and living organisms. These QDs appear to be promising candidates for biomedical applications such as drug delivery for enhanced chemotherapy or targeted delivery of light sensitive substances for photodynamic therapy.
- Full Text:
- Date Issued: 2014
Synthesis of ytterbium bisphthalocyanines
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189887 , vital:44943 , xlink:href="https://doi.org/10.1016/j.optmat.2014.05.013"
- Description: Herein we report on the syntheses, photophysico-chemical properties and nonlinear absorption parameters of bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-2-yloxy phthalocyaninato)} ytterbium (III) (3) and bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-4-yloxy phthalocyaninato)} ytterbium (III) (4). The fluorescence and singlet oxygen quantum yields obtained for complexes 3 and 4 are low. The triplet quantum yield obtained for complex 3 is high at ΦT = 0.89 whereas for complex 4 ΦT = 0.48. The third order optical susceptibility values are of the order: 10−11 esu (for complex 3), and 10−13 esu (for complex 4) while the hyperpolarizability values are of the order: 10−28 esu (for complex 3) and 10−31 esu (for complex 4). Complexes 3 and 4 show two-photon absorption coefficients of the order of 10−46 cm4 s/photon and 10−48 cm4 s/photon, and threshold intensities as low as 0.3 J cm−2 and 0.0045 J cm−2, respectively.
- Full Text:
- Date Issued: 2014
Glutathione capped CdTe@ ZnS quantum dots–zinc tetracarboxy phthalocyanine conjugates
- Authors: Sekhosana, Kutloana E , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193780 , vital:45395 , xlink:href="https://doi.org/10.1016/j.poly.2013.02.060"
- Description: Conjugates of zinc tetracarboxy phthalocyanine (ZnPc(COOH)4) with CdTe@ZnS–GSH quantum dots (QDs) were synthesized and characterized by several techniques including X-ray powder diffraction and infrared spectroscopy. There was an observed decrease in both the fluorescence quantum yields and lifetimes of the quantum dots when they were linked or mixed with ZnPc(COOH)4 due to Förster resonance energy transfer (FRET). The FRET behavior of CdTe@ZnS–GSH–ZnPc(COOH)4 conjugates was compared to that of CdTe@ZnS–GSH–ZnPc(COOH)8. Higher FRET efficiencies were observed for CdTe@ZnS–GSH–ZnPc(COOH)4-mixed or CdTe@ZnS–GSH–ZnPc(COOH)4-linked compared to the corresponding CdTe@ZnS–GSH–ZnPc(COOH)8-mixed or CdTe@ZnS–GSH–ZnPc(COOH)8-linked. Also CdTe@ZnS–GSH–ZnPc(COOH)4-mixed (containing coreshell QDs) showed higher FRET efficiency than CdTE–TGA–ZnPc(COOH)4-mixed containing core QDs. The FRET efficiencies were found to be 63% and 59% for the CdTe@ZnS–GSH–ZnPc(COOH)4-linked and CdTe@ZnS–GSH–ZnPc(COOH)4-mixed samples, respectively.
- Full Text:
- Date Issued: 2013