Synthesis, characterization and electrochemistry of phthalocyanine derivatives with biomedical applications
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Date
2016
Authors
Oosthuizen, Dina Naudé
Journal Title
Journal ISSN
Volume Title
Publisher
University of the Free State
Abstract
English: A series of metal-free phthalocyanines, with ethylene glycol and alkyl peripheral and nonperipheral
substituents, were synthesized and characterized with the aid of 1H NMR, IR and
UV/vis spectroscopy. The electrochemical study (cyclic voltammetry) showed smaller peak
potentials for phthalocyanines with shorter ethylene glycol substituents, thus the shorter the
ethylene glycol chain, the higher the electron density of the macrocycle.
Electrochemical (cyclic, square wave and linear sweep voltammetry) and computational
(including the determination of relevant geometries and molecular orbitals) studies were done
on a series of ruthenium phthalocyaninato complexes. A comparison of the peak oxidation
potential of the first experimental oxidation process and computed energy of the highest
occupied molecular orbitals (HOMO) for the series of (CO)RuPc, showed a linear
correlation..
An RC1 reactor was used to study the hydrogenation reaction of 4-nitrophthalonitrile as weak
as the oxidation reaction of 2,5-dihexylthiophene and 2,5didodecylthiophene utilizing
dimethyldioxirane of oxidizing agent. By making use of the RC1 reactor, the reactions were
followed kinetically and thermodynamically, yielding rate constants as well as reaction
enthalpies. These results were compared to theoretical reaction enthalpies determined by DFT
calculations. Good correlation was found between the experimentally obtained reaction
enthalpies and theoretical reaction enthalpies.
Afrikaans: ‘n Reeks van metaal-vrye phthalosianien komplekse met etileen glikol en alkiel periferiese en nie-periferiese substituente, is gesintetiseer en gekarakteriseer met behulp van 1H NMR, IR en UV/vis spektroskopie. ‘n Elektrochemiese studie met behulp van sikliese voltammetrie het gewys dat phthalosianiene met korter etileen glikol kettings kleiner piek potensiale het dus verhoog dit die elektron digtheid van die makrosikliese struktuur . ‘n Elektrochemiese (sikliese, vierkantige golf en lineêre golwing voltammetrie) en berekenings studies is gedoen op ‘n reeks van ruthenium phthalosianienato komplekse. ‘n Reglynige verband is gevind tussen die oksidasie potentiaal van die eerste eksperimentele oksidasie proses en die berekende energie van die hoogste besette molekulêre orbitaal (HOMO). ‘n RC1 reaktor studie iss gedoen op die hidrogeneringsreaksie van 4-nitrophthalonitriel, asook die oksidasie reaksie van 2,5-diheksieltiofeen en 2,5-didodesieltiofeen utilizing dimetieldioksiraan as oksideermiddel. Met behulp van die RC1 reaktor, is tempokonstantes en reaksie entalpieë kon bereken word vir elke reaksie. Hierdie resultate was gevergelyk met teoriese reaksie bereken vir elke reaksie. Die resultate is vergelyk met teoretiese reaksie entalpieë bereken deur DFT. ‘n Goeie verband is gevind tussen die eksperimentele en teoreties berekende reaksie entalpieë.
Afrikaans: ‘n Reeks van metaal-vrye phthalosianien komplekse met etileen glikol en alkiel periferiese en nie-periferiese substituente, is gesintetiseer en gekarakteriseer met behulp van 1H NMR, IR en UV/vis spektroskopie. ‘n Elektrochemiese studie met behulp van sikliese voltammetrie het gewys dat phthalosianiene met korter etileen glikol kettings kleiner piek potensiale het dus verhoog dit die elektron digtheid van die makrosikliese struktuur . ‘n Elektrochemiese (sikliese, vierkantige golf en lineêre golwing voltammetrie) en berekenings studies is gedoen op ‘n reeks van ruthenium phthalosianienato komplekse. ‘n Reglynige verband is gevind tussen die oksidasie potentiaal van die eerste eksperimentele oksidasie proses en die berekende energie van die hoogste besette molekulêre orbitaal (HOMO). ‘n RC1 reaktor studie iss gedoen op die hidrogeneringsreaksie van 4-nitrophthalonitriel, asook die oksidasie reaksie van 2,5-diheksieltiofeen en 2,5-didodesieltiofeen utilizing dimetieldioksiraan as oksideermiddel. Met behulp van die RC1 reaktor, is tempokonstantes en reaksie entalpieë kon bereken word vir elke reaksie. Hierdie resultate was gevergelyk met teoriese reaksie bereken vir elke reaksie. Die resultate is vergelyk met teoretiese reaksie entalpieë bereken deur DFT. ‘n Goeie verband is gevind tussen die eksperimentele en teoreties berekende reaksie entalpieë.
Description
Keywords
Dissertation (M.Sc. (Chemistry))--University of the Free State, 2016, Phthalocynines, DFT, RC1 reactor, Cyclic voltammetry