Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
The effects of silica based nanoparticles on the photophysicochemical properties, in vitro dark viability and photodynamic therapy study of zinc monocarboxyphenoxy phthalocyanine
- Authors: Oluwole, David O , Uddin, Imran , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240371 , vital:50828 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.07.002"
- Description: Aminopropyl triethoxysilane functionalized core SiO2 and core/shell ZnO/SiO2 nanoparticles (NP) were covalently linked to zinc monocarboxyphenoxy phthalocyanine (ZnMCPPc, complex 1) via amide bond formation. The photophysicochemical behavior, in vitro dark viability and photodynamic therapy (PDT) activity against human breast adenocarcinoma cell line (MCF-7 cells) of the conjugates were studied. The nanoconjugates showed enhanced photophysicochemical behavior as compared to complex 1 alone. Complex 1 showed higher dark toxicity against MCF-7 cells when compared to the conjugates. In the dark, complex 1 accounted for less than 50% viable cells at 28.6 μg/mL and 57.1 μg/mL compared to the conjugates which accounted for more than 50% cell viability at these concentrations. The in vitro dark viability and PDT activity of complex 1 was reduced in the presence of these nanoparticles.
- Full Text:
- Date Issued: 2016
The interaction between graphene quantum dots grafted with polyethyleneimine and Au@ Ag nanoparticles
- Authors: Achadu, Ojodomo John , Uddin, Imran , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188679 , vital:44775 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.03.016"
- Description: Graphene quantum dots grafted with polyethyleneimine (GQDs-PEI) and Au@Ag core-shell nanoparticles blend was demonstrated to be a novel biosensing nanoprobe for the rapid and highly sensitive detection of biothiols such as cysteine (Cys), homocysteine (Hcys) and glutathione (GSH). The fluorescence emission of GQDs-PEI was quenched efficiently upon interaction with Au@Ag core-shell nanoparticles. The quenched fluorescence emission of the GQDs-PEI was restored in the presence of the biothiols. The fluorimetric sensing is based on the strong affinity between the mercapto (SH) groups of the biothiols and the Au@Ag core-shell nanoparticles by which the interaction between GQDs-PEI and Au@Ag core-shell nanoparticles was disrupted with a consequent modulation (‘turn-on’) of the quenched GQDs-PEI emission. Thus, a new, simple, rapid and highly sensitive fluorescence nanoprobe for detecting biothiols has been developed in this work.
- 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
The photobleaching of the free and encapsulated metallic phthalocyanine and its effect on the photooxidation of simple molecules
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. 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.
- Full Text:
- Date Issued: 2016
“Turn on” fluorescence enhancement of Zn octacarboxyphthaloyanine-graphene oxide conjugates by hydrogen peroxide
- Authors: Shumba, Munyaradzi , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190438 , vital:44994 , xlink:href="https://doi.org/10.1016/j.jlumin.2015.11.001"
- Description: Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates were characterized by absorption spectroscopy, transmission electron microscopy, fluorescence spectroscopy, X-ray diffraction, thermo gravimetric analysis and X-ray photon spectroscopy. The presence of reduced graphene oxide or graphene oxide resulted in the quenching (turn on) of Zn octacarboxy phthalocyanine fluorescence which can be explained by photoinduced electron transfer. Zn octacarboxy phthalocyaninereduced graphene oxide or graphene oxide conjugates “turned on” fluorescence showed a linear response to hydrogen peroxide hence their potential to be used as sensors. The nanoprobe developed showed high selectivity towards hydrogen peroxide in the presence of physiological interferences.
- Full Text:
- Date Issued: 2016
“Turn on” fluorescence enhancement of Zn octacarboxyphthaloyanine-graphene oxide conjugates by hydrogen peroxide
- Authors: Shumba, Munyaradzi , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240875 , vital:50881 , xlink:href="https://doi.org/10.1016/j.jlumin.2015.11.001"
- Description: Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates were characterized by absorption spectroscopy, transmission electron microscopy, fluorescence spectroscopy, X-ray diffraction, thermo gravimetric analysis and X-ray photon spectroscopy. The presence of reduced graphene oxide or graphene oxide resulted in the quenching (turn on) of Zn octacarboxy phthalocyanine fluorescence which can be explained by photoinduced electron transfer. Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates “turned on” fluorescence showed a linear response to hydrogen peroxide hence their potential to be used as sensors. The nanoprobe developed showed high selectivity towards hydrogen peroxide in the presence of physiological interferences.
- Full Text:
- Date Issued: 2016
(Ferrocenylpyrazolyl) zinc (II) benzoates as catalysts for the ring opening polymerization of ε-caprolactone
- Authors: Obuah, Collins , Lochee, Yemanlall , Jordaan, Johan H L , Otto, Daniel P , Nyokong, Tebello , Darkwa, James
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189515 , vital:44853 , xlink:href="https://doi.org/10.1016/j.poly.2015.02.007"
- Description: The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3 COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of e-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1 H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 107 h1 mol1 at 110 C.
- Full Text:
- Date Issued: 2015
A comparative photophysicochemical study of phthalocyanines encapsulated in core–shell silica nanoparticles
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189708 , vital:44924 , xlink:href="https://doi.org/10.1016/j.saa.2014.08.062"
- Description: This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4- carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix.
- Full Text:
- Date Issued: 2015
Characterization of porphyrin nanorods on fluorine doped tin oxide glass sheet
- Authors: George, Reama C , Falgenhauer, Jane , Geis, Clemens , Nyokong, Tebello , Schlettwein, Derck
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193542 , vital:45344 , xlink:href="https://doi.org/10.1142/S1088424615500923"
- Description: Porphyrin nanorods (PNR) have been fabricated by electrostatic self-assembly of two oppositely charged porphyrin molecules. The free base meso-tetra-(4-phenylsulphonate) porphyrin (TPPS4)4) served as negatively charged counterpart for the positively charged metallo meso-tetra(4-NN-methylpyridyl) porphyrins (MTM’PyP) with either Sn, Co, Mn or In as central metal M. Films of PNR were prepared on fluorine doped tin oxide glass sheets (FTO) by using a drop-dry method. The electronic spectra revealed J-aggregation of the charged molecules for the colloid PNR as well as for the films. Transmission electron microscopy confirmed the formation of porphyrin nanorods. The laser microscope and scanning electron microscope (SEM) images of the PNR/FTO films showed the formation of three kinds of structures in the films which consist of differently branched or linear needles with their main axis grown in the direction of the solvent flow during preparation. During cyclic voltammetry either applying negative potentials from 0.0 V to -1.0 V or positive potentials from 0.0 V to ++2.2 V irreversible reduction or oxidation reactions were detected for the films. Consistently, SEM images taken following cyclic voltammetry showed the disintegration of the PNR on the films into smaller subunits. Spectroelectrochemical measurements showed the formation of porphyrin anionic radicals during oxidation by a decrease in the absorption intensities and broadening of spectra with an additional band appearing around 900 nm. A similar trend was observed when negative potentials were applied but in this case the cationic radical was produced. In both cases the decrease of the intensity of the J-aggregate confirms a loss of intermolecular coupling, again consistent with the smaller subunits observed in SEM analysis.
- Full Text:
- Date Issued: 2015
Comparative electrocatalytic studies of nanocomposites of mixed and covalently linked multiwalled carbon nanotubes and 4-(4, 6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt (II)
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189285 , vital:44834 , xlink:href="https://doi.org/10.1016/j.poly.2015.05.038"
- Description: Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards L-cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite.
- Full Text:
- Date Issued: 2015
Effects of differently shaped silver nanoparticles on the photophysics of pyridylsulfanyl-substituted phthalocyanines
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines.
- Full Text:
- Date Issued: 2015
Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines
- Authors: D'Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189741 , vital:44927 , xlink:href="https://doi.org/10.1016/j.poly.2014.09.012"
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis- (mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods.
- Full Text:
- Date Issued: 2015
Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
Electrode modification using alkynyl substituted Fe (II) phthalocyanine via electrografting and click chemistry for electrocatalysis
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189296 , vital:44835 , xlink:href="https://doi.org/10.1002/elan.201500212"
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM.
- Full Text:
- Date Issued: 2015
Enhanced optical limiting behaviour of indium phthalocyanine derivatives when in solution or embedded in poly (acrylic acid) or poly (methyl methacrylate) polymers
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189445 , vital:44847 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.02.003"
- Description: The optical limiting performance of indium phthalocyanine-based polymer thin-films with large nonlinear absorption coefficients (βeff) and low limiting threshold intensity (Ilim) are described. The absorption cross-sections and the population dynamics of the excited states are also reported. The excited state absorption cross-sections (σexc) are shown to depend on the transition moment between the T1 and T2 states. βeff values have been shown to be related to the population density of the molecules in the T1 state. The improved optical limiting performance recorded for the investigated phthalocyanine complexes in the presence of polymer matrices has been attributed to the aggregation effects of the complexes in the polymer thin-films. The optical properties of the indium phthalocyanine moieties were found to possess robust sensitivity to a change of the polymer materials.
- Full Text:
- Date Issued: 2015
Enhanced triplet state parameters for zinc carboxy phenoxy phthalocyanine following conjugation to ascorbic acid
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189348 , vital:44839 , xlink:href="https://doi.org/10.1016/j.poly.2015.01.032"
- Description: Zinc phthalocyanine bearing four ascorbic acid units (formed via ester bond between zinc carboxy phenoxy phthalocyanines and ascorbic acid) was synthesized and characterized using different spectroscopic methods. The complex (with or without ascorbic acid) was further adsorbed onto single walled carbon nanotubes (SWCNTs) and further characterized using Raman spectroscopy, X-ray diffractometry, transmission electron microscopy and thermogravimetric analysis. The photophysical properties of the complexes were studied. The synthesized complex showed better photophysical properties when compared to the carboxy phenoxy phthalocyanines alone, this is evident in the increase of the triplet quantum yields (ΦT), triplet life-times (τT) and singlet oxygen quantum yields (ΦΔ). The zinc phthalocyanines bearing ascorbic acid showed improved triplet life-times even in the presence of SWCNTs.
- Full Text:
- Date Issued: 2015
Enhanced triplet state yields in aqueous media of asymmetric zinc phthalocyanines when conjugated to silver nanoflowers
- Authors: D'Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmus, Mahmut , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189099 , vital:44816 , xlink:href="https://doi.org/10.1016/j.poly.2015.08.017"
- Description: Novel low symmetry water-soluble zinc phthalocyanines (ZnPcs, complexes 1 and 2) were synthesized and then mixed with silver nanoflowers. Photophysical and photochemical studies were performed in order to determine the efficiency of complexes 1 and 2 as photosensitizers when alone and when combined with the silver nanoflowers. The Pcs show low fluorescence quantum yields and excellent triplet quantum yields of 0.78 (for 1) and 0.66 (for 2) in aqueous media. The triplet quantum yield values increased to 0.80 and 0.89, respectively, in the presence of silver nanoflowers. Long triplet lifetimes ranging from 180 to 200 μs in DMSO were obtained for complexes 1, 2 and their conjugates with silver nanoflowers.
- Full Text:
- Date Issued: 2015
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
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- Date Issued: 2015