Effects of the number of ring substituents of cobalt carboxyphthalocyanines on the electrocatalytic detection of nitrite, cysteine and melatonin
- Matemadombo, Fungisai, Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Matemadombo, Fungisai , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263408 , vital:53625 , xlink:href="https://doi.org/10.1142/S108842460900125X"
- Description: Cobalt phthalocyanine (CoPc), cobalt tetracarboxy phthalocyanine (CoTCPc) and cobalt octacarboxy phthalocyanine (CoOCPc), adsorbed onto glassy carbon electrodes, have been used for the electrocatalytic detection of nitrite, L-cysteine and melatonin. The modified electrodes electrocatalytically detected nitrite around 800 mV vs.Ag|AgCl, a value less positive compared to that of an unmodified glassy carbon electrode (at 950 mV vs.Ag|AgCl) and also gave detection limits in the 10-7 M range for nitrite detection. L-cysteine was detected by the modified electrodes at potentials between 0.50 to 0.65 V vs.Ag|AgCl, with L-cysteine detection limits also in the 10-7 M range. The detection limits for melatonin ranged from 10-7 to 10-6 M. CoPc-modified electrodes displayed good separation of interferents (tryptophan and ascorbic acid) in the presence of melatonin. Analyses of commercial melatonin tablets using modified electrodes gave excellent agreement with manufacturer's value for all modified electrodes of this work.
- Full Text:
- Date Issued: 2009
- Authors: Matemadombo, Fungisai , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263408 , vital:53625 , xlink:href="https://doi.org/10.1142/S108842460900125X"
- Description: Cobalt phthalocyanine (CoPc), cobalt tetracarboxy phthalocyanine (CoTCPc) and cobalt octacarboxy phthalocyanine (CoOCPc), adsorbed onto glassy carbon electrodes, have been used for the electrocatalytic detection of nitrite, L-cysteine and melatonin. The modified electrodes electrocatalytically detected nitrite around 800 mV vs.Ag|AgCl, a value less positive compared to that of an unmodified glassy carbon electrode (at 950 mV vs.Ag|AgCl) and also gave detection limits in the 10-7 M range for nitrite detection. L-cysteine was detected by the modified electrodes at potentials between 0.50 to 0.65 V vs.Ag|AgCl, with L-cysteine detection limits also in the 10-7 M range. The detection limits for melatonin ranged from 10-7 to 10-6 M. CoPc-modified electrodes displayed good separation of interferents (tryptophan and ascorbic acid) in the presence of melatonin. Analyses of commercial melatonin tablets using modified electrodes gave excellent agreement with manufacturer's value for all modified electrodes of this work.
- Full Text:
- Date Issued: 2009
Electro-catalyzed oxidation of reduced glutathione and 2-mercaptoethanol by cobalt phthalocyanine-containing screen printed graphite electrodes
- Sehlotho, Nthapo, Griveau, Sophie, Ruillé, Nadine, Boujtita, Mohammed, Nyokong, Tebello, Bedioui, Fethi
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Ruillé, Nadine , Boujtita, Mohammed , Nyokong, Tebello , Bedioui, Fethi
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265935 , vital:53902 , xlink:href="https://doi.org/10.1016/j.msec.2007.10.054"
- Description: Electro-catalytic behavior of screen printed graphite electrodes modified with cobalt phthalocyanine (CoPc) towards the oxidation of reduced glutathione (GSH) and 2-mercaptoethanol (2-ME) is reported. We find, by using cyclic voltammetry, that the oxidation of 2-ME occurs at 0.2 V vs Ag/AgCl and − 0.3 vs Ag/AgCl V at pH = 7 and pH = 13, respectively and that of GSH occurs at 0.4 V vs Ag/AgCl and 0.0 V vs Ag/AgCl at pH = 7 and 13, respectively. The electro-catalytic activity depends on the method of electrode modification and the amount of catalyst incorporated in the ink used to fabricate the SPCEs. The highest activity was obtained with electrodes prepared with 2.5% (w:w) of CoPc.
- Full Text:
- Date Issued: 2008
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Ruillé, Nadine , Boujtita, Mohammed , Nyokong, Tebello , Bedioui, Fethi
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265935 , vital:53902 , xlink:href="https://doi.org/10.1016/j.msec.2007.10.054"
- Description: Electro-catalytic behavior of screen printed graphite electrodes modified with cobalt phthalocyanine (CoPc) towards the oxidation of reduced glutathione (GSH) and 2-mercaptoethanol (2-ME) is reported. We find, by using cyclic voltammetry, that the oxidation of 2-ME occurs at 0.2 V vs Ag/AgCl and − 0.3 vs Ag/AgCl V at pH = 7 and pH = 13, respectively and that of GSH occurs at 0.4 V vs Ag/AgCl and 0.0 V vs Ag/AgCl at pH = 7 and 13, respectively. The electro-catalytic activity depends on the method of electrode modification and the amount of catalyst incorporated in the ink used to fabricate the SPCEs. The highest activity was obtained with electrodes prepared with 2.5% (w:w) of CoPc.
- Full Text:
- Date Issued: 2008
Electrochemical and electrocatalytic properties of α-substituted manganese and titanium phthalocyanines
- Nombona, Nolwazi, Tau, Prudence, Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Tau, Prudence , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268587 , vital:54212 , xlink:href="https://doi.org/10.1016/j.electacta.2007.11.046"
- Description: This work reports on the synthesis of manganese and titanium phthalocyanine complexes that are tetra-substituted at four non-peripheral positions with amino ligands. The complexes are investigated for the first time for their electrochemical properties using cyclic voltammetry, rotating disc electrode voltammetry and spectroelectrochemistry. Electropolymerisation on a glassy carbon electrode was performed with ease and the modified electrodes were investigated for electrocatalysis of nitrite oxidation. Nitrite oxidation to nitrate is confirmed from the transfer of a total of two electrons.
- Full Text:
- Date Issued: 2008
- Authors: Nombona, Nolwazi , Tau, Prudence , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268587 , vital:54212 , xlink:href="https://doi.org/10.1016/j.electacta.2007.11.046"
- Description: This work reports on the synthesis of manganese and titanium phthalocyanine complexes that are tetra-substituted at four non-peripheral positions with amino ligands. The complexes are investigated for the first time for their electrochemical properties using cyclic voltammetry, rotating disc electrode voltammetry and spectroelectrochemistry. Electropolymerisation on a glassy carbon electrode was performed with ease and the modified electrodes were investigated for electrocatalysis of nitrite oxidation. Nitrite oxidation to nitrate is confirmed from the transfer of a total of two electrons.
- Full Text:
- Date Issued: 2008
The synthesis and electrochemical behaviour of water soluble manganese phthalocyanines: Anion radical versus Mn(I) species
- Sehlotho, Nthapo, Durmuş, Mahmut, Ahsen, N, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Durmuş, Mahmut , Ahsen, N , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6596 , http://hdl.handle.net/10962/d1004345
- Description: The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents.
- Full Text:
- Date Issued: 2008
- Authors: Sehlotho, Nthapo , Durmuş, Mahmut , Ahsen, N , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6596 , http://hdl.handle.net/10962/d1004345
- Description: The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents.
- Full Text:
- Date Issued: 2008
Cobalt Phthalocyanine Molecular Electrode for the Electrochemical Investigation of the Release of Glutathione upon Copper-Catalyzed Decomposition of S-Nitrosoglutathione
- Sehlotho, Nthapo, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281201 , vital:55701 , xlink:href="https://doi.org/10.1002/elan.200603656"
- Description: Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.
- Full Text:
- Date Issued: 2007
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281201 , vital:55701 , xlink:href="https://doi.org/10.1002/elan.200603656"
- Description: Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.
- Full Text:
- Date Issued: 2007
Effects of ring substituents on electrocatalytic activity of manganese phthalocyanines towards the reduction of molecular oxygen
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6594 , http://hdl.handle.net/10962/d1004343
- Description: Reduction of oxygen electrocatalyzed by adsorbed films of manganese phthalocyanine complexes is reported. The complexes studied were: manganese phthalocyanine (MnPc, 1); manganese tetraamino phthalocyanine (MnTAPc, 2); manganese tetrapentoxy pyrrole phthalocyanine (MnTPePyrPc, 3); manganese tetra phenoxy pyrrole phthalocyanine (MnTPPyrPc, 4); manganese tetra mercaptopyrimidine phthalocyanine (MnTMPyPc, 5) and manganese tetra ethoxy thiophene phthalocyanine (MnTETPc, 6). The reaction was conducted in buffer solutions of pH range 1–12. Rotating disk electrode voltammetry revealed two electron reduction in acidic and slightly alkaline media due to the formation of hydrogen peroxide. In highly basic media, water is the major product formed via four electron transfer. The reaction was found to be first order in the diffusing analyte oxygen.
- Full Text:
- Date Issued: 2006
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6594 , http://hdl.handle.net/10962/d1004343
- Description: Reduction of oxygen electrocatalyzed by adsorbed films of manganese phthalocyanine complexes is reported. The complexes studied were: manganese phthalocyanine (MnPc, 1); manganese tetraamino phthalocyanine (MnTAPc, 2); manganese tetrapentoxy pyrrole phthalocyanine (MnTPePyrPc, 3); manganese tetra phenoxy pyrrole phthalocyanine (MnTPPyrPc, 4); manganese tetra mercaptopyrimidine phthalocyanine (MnTMPyPc, 5) and manganese tetra ethoxy thiophene phthalocyanine (MnTETPc, 6). The reaction was conducted in buffer solutions of pH range 1–12. Rotating disk electrode voltammetry revealed two electron reduction in acidic and slightly alkaline media due to the formation of hydrogen peroxide. In highly basic media, water is the major product formed via four electron transfer. The reaction was found to be first order in the diffusing analyte oxygen.
- Full Text:
- Date Issued: 2006
Electrocatalysis of oxidation of 2-mercaptoethanol, L-cysteine and reduced glutathione by adsorbed and electrodeposited cobalt tetra phenoxypyrrole and tetra ethoxythiophene substituted phthalocyanines
- Sehlotho, Nthapo, Nyokong, Tebello, Zagal, Jose H, Bedioui, Fethi
- Authors: Sehlotho, Nthapo , Nyokong, Tebello , Zagal, Jose H , Bedioui, Fethi
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6593 , http://hdl.handle.net/10962/d1004342
- Description: Catalytic activity of cobalt tetra ethoxythiophene and cobalt tetra phenoxypyrrole phthalocyanine complexes towards oxidation of 2-mercaptoethanol, L-cysteine and reduced glutathione is reported. It was found that the activity of the complexes depends on the substitution of the phthalocyanine ring, pH, film thickness and method of electrode modification. The high electrocatalytic activity obtained with adsorbed complexes in alkaline medium clearly demonstrates the necessity of modifying bare carbon electrodes to endow them with the desired behaviour.
- Full Text:
- Date Issued: 2006
- Authors: Sehlotho, Nthapo , Nyokong, Tebello , Zagal, Jose H , Bedioui, Fethi
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6593 , http://hdl.handle.net/10962/d1004342
- Description: Catalytic activity of cobalt tetra ethoxythiophene and cobalt tetra phenoxypyrrole phthalocyanine complexes towards oxidation of 2-mercaptoethanol, L-cysteine and reduced glutathione is reported. It was found that the activity of the complexes depends on the substitution of the phthalocyanine ring, pH, film thickness and method of electrode modification. The high electrocatalytic activity obtained with adsorbed complexes in alkaline medium clearly demonstrates the necessity of modifying bare carbon electrodes to endow them with the desired behaviour.
- Full Text:
- Date Issued: 2006
Electrocatalytic oxidation of thiocyanate, L-cysteine and 2-mercaptoethanol by self-assembled monolayer of cobalt tetraethoxy thiophene phthalocyanine
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283814 , vital:55993 , xlink:href="https://doi.org/10.1016/j.electacta.2005.12.024"
- Description: Catalytic activity of a self-assembled monolayer (SAM) of cobalt tetra ethoxythiophene phthalocyanine (CoTEThPc-SAM) complex towards oxidation of thiocyanate (SCN−), L-cysteine (CYS) and 2-mercaptoethanol (2-ME) is reported. The oxidation of thiocyanate occurs via a two electron transfer, whereas L-cysteine and 2-ME require 1 electron. The oxidation of thiocyanate is catalysed by ring based processes, while L-cysteine is catalysed by both CoIII/CoII process and by ring based processes. 2-ME is catalysed by CoIII/CoII process. The oxidation of thiocyanate on CoTEThPc was performed in acid media instead of basic media commonly employed. The reaction order was found to be unity for all the analytes, showing that only one molecule of analyte interacts with one molecule of the catalyst during the rate determining step.
- Full Text:
- Date Issued: 2006
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283814 , vital:55993 , xlink:href="https://doi.org/10.1016/j.electacta.2005.12.024"
- Description: Catalytic activity of a self-assembled monolayer (SAM) of cobalt tetra ethoxythiophene phthalocyanine (CoTEThPc-SAM) complex towards oxidation of thiocyanate (SCN−), L-cysteine (CYS) and 2-mercaptoethanol (2-ME) is reported. The oxidation of thiocyanate occurs via a two electron transfer, whereas L-cysteine and 2-ME require 1 electron. The oxidation of thiocyanate is catalysed by ring based processes, while L-cysteine is catalysed by both CoIII/CoII process and by ring based processes. 2-ME is catalysed by CoIII/CoII process. The oxidation of thiocyanate on CoTEThPc was performed in acid media instead of basic media commonly employed. The reaction order was found to be unity for all the analytes, showing that only one molecule of analyte interacts with one molecule of the catalyst during the rate determining step.
- Full Text:
- Date Issued: 2006
Catalytic activity of iron and cobalt phthalocyanine complexes towards the oxidation of cyclohexene using tert-butylhydroperoxide and chloroperoxybenzoic acid
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
- Full Text:
- Date Issued: 2004
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
- Full Text:
- Date Issued: 2004
Zinc phthalocyanine photocatalyzed oxidation of cyclohexene
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289399 , vital:56629 , xlink:href="https://doi.org/10.1016/j.molcata.2004.05.010"
- Description: Cyclohexene photooxidation catalyzed by zinc phthalocyanine (ZnPc) using either red or white light results in the formation of cyclohexenone, cyclohexenol, trans-cyclohexanediol, cyclohexene oxide and cyclohexene hydroperoxide. The product yield increased as follows: cyclohexenone > cyclohexenol > trans-cyclohexanediol > cyclohexene oxide > cyclohexene hydroperoxide. The mechanism for the formation of these products involves both singlet oxygen and radicals (Type II and Type I mechanisms, respectively). The catalyst degraded slowly when low light intensities were employed. The product yields were found to depend on the light intensity, the nature of solvent, irradiation time and the rate of photodegradation of the catalyst.
- Full Text:
- Date Issued: 2004
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289399 , vital:56629 , xlink:href="https://doi.org/10.1016/j.molcata.2004.05.010"
- Description: Cyclohexene photooxidation catalyzed by zinc phthalocyanine (ZnPc) using either red or white light results in the formation of cyclohexenone, cyclohexenol, trans-cyclohexanediol, cyclohexene oxide and cyclohexene hydroperoxide. The product yield increased as follows: cyclohexenone > cyclohexenol > trans-cyclohexanediol > cyclohexene oxide > cyclohexene hydroperoxide. The mechanism for the formation of these products involves both singlet oxygen and radicals (Type II and Type I mechanisms, respectively). The catalyst degraded slowly when low light intensities were employed. The product yields were found to depend on the light intensity, the nature of solvent, irradiation time and the rate of photodegradation of the catalyst.
- Full Text:
- Date Issued: 2004
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