Effect of nanoparticles on the photophysicochemical behaviour of metallophthalocyanines

The synthesis, spectroscopic characterization, and studies of the photophysicochemical behaviour of selective anionic, cationic and neutral metallophthallocyanine (MPc) complexes were carried out and the results are presented herein. Studies on the effect of the central metal ion, the solvent used and the presence of nanoparticles on the photophysicochemical properties were conducted. The findings showed that the photophysicochemical parameters were mostly enhanced in the presence of central metal ions of high atomic numbers and also in the presence of nanoparticles. It was also observed that solvents that encouraged the monomericity of the MPc complexes also lead to improved photophysical and photochemical behaviour. CdTe quantum dots (QDs) stabilized with mercaptocarbonic acids were also observed to cause stimulated emission of the MPcs through Förster resonance energy transfer (FRET) thus acting as energy donors while the respective MPc acted as energy acceptors in all the FRET studies. FRET was observed following the photoexcitation of QDs for all monomeric anionic MPcs but it was also shown to occur for some cationic MPcs in organic media. Both the substituent and solvent used were found to exert a strong influence on the occurrence of FRET. Other cationic MPcs however showed different behaviour in the presence of the meraptocarbonic stabilized CdTe QDs; with the cationic porphyrazine giving clear indications of Pc ring reduction. The rest of the cationic MPcs did not give clear evidence of Pc ring reduction, instead they showed signs of aggregate formation possibly from the assembly of electrostatic ion pair complexes which could result in reduction of the quaternized pyridinium ring of the substituent. Both the QDs and the MPc complex emission spectra were significantly quenched for each in the presence of the other. Stern-Volmer quenching studies indicated that both static and dynamic quenching of the QDs in the presence of MPcs took place. The fluorescence lifetimes of the mercaptopropionic acid (MPA) capped CdTe QDs in the presence of various MPc complexes showed quenching of mostly the longer lifetimes of the QDs in the presence of MPcs suggesting that the surface defects and states are involved in the interaction of the QDs and MPcs. An MPc complex terminating in thio tethers was employed in the conjugation to AuNPs. Spectroscopic and microscopic studies confirmed the formation of the MPc-AuNP conjugate which was also shown to exhibit improved photophysicochemical properties compared to the free MPc

The photophysical studies of a mixture of CdTe quantum dots and negatively charged zinc phthalocyanines

Fluorescence resonance energy transfer (FRET) studies were carried out with quantum dots capped with thioglycolic acid (TGA) and 2-mercaptoethanol (2-ME) and negatively charged phthalocyanines {Zn tetracarboxy (ZnTCPc), Zn octacarboxy (ZnOCPc) and Zn tetrasulfo (ZnTSPc) phthalocyinines} in a 0.1 NaOH:EtOH (50:50) solvent mixture. The best overlap between emission spectra of the donor (QDs) and the absorption spectra of the acceptor (ZnPc derivatives) was observed for TGA capped QDs, very little overlap was obtained for 2-ME QDs. ZnTSPc gave the highest FRET efficiency (0.3), with ZnOCPc and ZnTCPc giving a FRET efficiency of 0.2. The ΦT values of the MPcs generally decreased in the presence of the QD whereas the triplet lifetimes (τT) of the ZnPc derivatives were higher in the presence of QDs

Opposing responses elicited by positively charged phthalocyanines in the presence of CdTe quantum dots

Tetrapositively charged phthalocyanines and CdTe quantum dots (QDs) capped with thioglycolic acid (TGA) and mercaptopropionic acid (MPA) were synthesized. The response of the tetrapositively charged zinc phthalocyanines in the presence of quantum dots was studied. Aggregation and charge transfer were observed for [tetramethyl-2,(3)-[tetra-(2-mercaptopyridinephthalocyaninato)]zinc(II)]4+ (TmTMPyZnPc), however aggregation proved to be the more prominent process of the two. Fluorescence resonance energy transfer (FRET) was observed with [tetramethyl-2,(3)-[tetra-(2- pyridyloxyphthalocyaninato)]zinc(II)]4+ (TmTPyZnPc). In the FRET study the efficiency of FRET with TmTPyZnPc was determined to be 21% for both MPA and TGA capped CdTe QDs. For the charge transfer study the fluorescence of the quantum dots was quenched by the TmTMPyZnPc used, and from these quenching studies the quenching constants, binding constants and number of binding sites on the quantum dots were determined

Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines

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

Voltammetry and electrochemical impedance spectroscopy of gold electrodes modified with CdTe quantum dots and their conjugates with nickel tetraamino phthalocyanine

This work reports on the synthesis of conjugates of cadmium telluride quantum dots (CdTe-QDs) caped with thioglycolic acid and peripherally substituted nickel tetraamino phthalocyanine (NiTAPc) complex. The conjugates are characterized using cyclic (CV) and differential pulse (DPV) voltammetries, electrochemical impedance spectroscopy, X-ray powder diffraction, infrared spectroscopy, Raman spectroscopy, atomic force microscopy and time correlated single photon counting. CV and DPV show that NiTAPc stabilizes the CdTe QDs against oxidation to metallic products

Spontaneous charge transfer between zinc tetramethyl-tetra-2, 3-pyridinoporphyrazine and CdTe and ZnS quantum dots

Zinc tetramethyl-tetra-2,3-pyridinoporphyrazine (ZnTmtppa(-2)) gets reduced to the ZnTmtppa(-3) species on interaction with CdTe QDs capped with 2-mercaptoethanol (2-ME) or thioglycolic acid (TGA) and ZnS QDs capped with 2-ME. The interaction occurs without photolysis. The fluorescence of the QDs is quenched by ZnTmtppa resulting in large quenching constants. Binding of ZnTmtppa to QDs occurs with two molecules of the former binding to the latter

Effects of gold nanoparticle shape on the aggregation and fluorescence behaviour of water soluble zinc phthalocyanines

The absorption and fluorescence response as well as the fluorescence quantum yields and lifetimes of sulfonated phthalocyanines and alkyl carboxylic acid substituted zinc phthalocyanines in the presence of differently shaped water soluble gold nanoparticles were studied. The respective phthalocyanines are known to be highly aggregated in water, which is reported to markedly reduce the excited state lifetimes. This paper shows that in the presence of star shaped gold nanoparticles, the degree of phthalocyanine aggregation in water is greatly reduced, but the aggregation status of the phthalocyanines does not change for spherical Au nanoparticles. Since gold nanoparticles have already proven to be useful in numerous nanomedicinal and nanomedical applications, the disaggregation of phthalocyanines is an added advantage

Solvent and central metal effects on the photophysical and photochemical properties of peripherally tetra mercaptopyridine substituted metallophthalocyanines

The synthesis of peripherally tetra 2-mercaptopyridine substituted phthalocyanines containing Si, Ga, Sn and In as central metal ions is reported for the first time in this study. Photophysical and photochemical studies were carried out on these compounds in order to determine the potential of the complexes as photosensitizers for use in photodynamic therapy. Fluorescence quantum yields (ΦF) ranged from 0.012 to 0.2 and triplet quantum yields (ΦT) from 0.54 to 0.89 in dimethylformamide (DMF) and from 0.65 to 0.93 in dimethylsulfoxide (DMSO). The triplet lifetimes ranged from 20 to 130 μs, the low values are due to the heavy atom effects of the central metal. The triplet lifetimes were larger in DMSO when compared with DMF

Effect of nanoparticles on the photophysicochemical behaviour of metallophthalocyanines

The synthesis, spectroscopic characterization, and studies of the photophysicochemical behaviour of selective anionic, cationic and neutral metallophthallocyanine (MPc) complexes were carried out and the results are presented herein. Studies on the effect of the central metal ion, the solvent used and the presence of nanoparticles on the photophysicochemical properties were conducted. The findings showed that the photophysicochemical parameters were mostly enhanced in the presence of central metal ions of high atomic numbers and also in the presence of nanoparticles. It was also observed that solvents that encouraged the monomericity of the MPc complexes also lead to improved photophysical and photochemical behaviour. CdTe quantum dots (QDs) stabilized with mercaptocarbonic acids were also observed to cause stimulated emission of the MPcs through Förster resonance energy transfer (FRET) thus acting as energy donors while the respective MPc acted as energy acceptors in all the FRET studies. FRET was observed following the photoexcitation of QDs for all monomeric anionic MPcs but it was also shown to occur for some cationic MPcs in organic media. Both the substituent and solvent used were found to exert a strong influence on the occurrence of FRET. Other cationic MPcs however showed different behaviour in the presence of the meraptocarbonic stabilized CdTe QDs; with the cationic porphyrazine giving clear indications of Pc ring reduction. The rest of the cationic MPcs did not give clear evidence of Pc ring reduction, instead they showed signs of aggregate formation possibly from the assembly of electrostatic ion pair complexes which could result in reduction of the quaternized pyridinium ring of the substituent. Both the QDs and the MPc complex emission spectra were significantly quenched for each in the presence of the other. Stern-Volmer quenching studies indicated that both static and dynamic quenching of the QDs in the presence of MPcs took place. The fluorescence lifetimes of the mercaptopropionic acid (MPA) capped CdTe QDs in the presence of various MPc complexes showed quenching of mostly the longer lifetimes of the QDs in the presence of MPcs suggesting that the surface defects and states are involved in the interaction of the QDs and MPcs. An MPc complex terminating in thio tethers was employed in the conjugation to AuNPs. Spectroscopic and microscopic studies confirmed the formation of the MPc-AuNP conjugate which was also shown to exhibit improved photophysicochemical properties compared to the free MPc

Voltammetry and electrochemical impedance spectroscopy of gold electrodes modified with CdTe quantum dots and their conjugates with nickel tetraamino phthalocyanine

This work reports on the synthesis of conjugates of cadmium telluride quantum dots (CdTe-QDs) caped with thioglycolic acid and peripherally substituted nickel tetraamino phthalocyanine (NiTAPc) complex. The conjugates are characterized using cyclic (CV) and differential pulse (DPV) voltammetries, electrochemical impedance spectroscopy, X-ray powder diffraction, infrared spectroscopy, Raman spectroscopy, atomic force microscopy and time correlated single photon counting. CV and DPV show that NiTAPc stabilizes the CdTe QDs against oxidation to metallic products