Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines

The review focuses on the photochemical (singlet oxygen and photobleaching quantum yields) and photophysical (triplet quantum yields and lifetimes and fluorescence lifetimes) properties of metallophthalocyanine complexes containing main group metals (Zn, Al, Ge, Si, Sn, Ga and In) and some unmetallated phthalocyanine complexes. Five tables containing photophysical and photochemical data for sulfonated phthalocyanines, tetra-, octa-substituted and unsubstituted phthalocyanines in a variety of solvents, are included in the review

Tebello Nyokong’s Letter to her 18-year-old Self

Dr. Nyokong’s is the director of the Nanotechnology Innovation Center at Rhodes University, South Africa and the first South African scientist to win the L’Oréal-UNESCO award for women in science. Her research focus on the development of molecules similar to the ones used to dye blue jeans, which can be used as chemical sensors to detect disease-related molecules and organisms, as an alternative to chemotherapy for the treatment of cancer and for environmental clean-up. [Don't miss the video at the end where she talks about her path and research]

Synthesis, photophysicochemical and photodynamic antimicrobial chemotherapy studies of indium pyridyl phthalocyanines: Charge versus bridging atom

2(3), 9(10), 16(17), 23(24)-Octapyridylsulfanyl phthalocyaninato chloroindium(III) (complex 1a) and its quaternized derivative 2(3), 9(10), 16(17), 23(24)-octamethylpyridylsulfanyl phthalocyaninato chloroindium (III) (complex 1b) were synthesised. The triplet quantum yields were 0.53 and 0.48 while the singlet oxygen quantum yields were 0.46 and 0.33 in DMF for 1a and 1b, respectively. The photodynamic antimicrobial chemotherapy (PACT) activity of 1b (containing 8 positive charges) was compared to those of 9(10),16(17),23(24)-tri-N-methyl-4-pyridylsulfanyl-2(3)-(4-aminophenoxy) phthalocyaninato chloro indium(III) triiodide (2) (containing 3 positive charges) and 2-[4-(N-Methylpyridyloxy) phthalocyaninato] chloroindium (III) iodide (3) (containing 4 positive charges). Complex 1b gave log reductions of 4.21, 8.30 and 3.21 for Gram(−) E. coli, Gram(+) S. aureus and C. albicans, respectively. When comparing 1b, 2 and 3, the largest log reductions for E. coli were obtained for complex 3 containing four positive charges hence showing it is not always the charge that determines the PACT activity, but the bridging atom in the phthalocyanine plays a role

Photophysicochemical and fFluorescence quenching studies of benzyloxyphenoxy substituted zinc phthalocyanines

Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications

The synthesis and photophysical properties of water soluble tetrasulfonated, octacarboxylated and quaternised 2,(3)-tetra-(2 pyridiloxy) Ga phthalocyanines

The photophysical behaviour of chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine (ClGaT-2-PyPc) and its quaternised derivative were compared with that of the water soluble anionic tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydoxy gallium octacarboxy phthalocyanine ((OH)GaOCPc). Although both the quaternised compound and the tetrasulfonated gallium phthalocyanine aggregated in aq. solution at pH 11, resulting in low fluorescence and triplet yields, the presence of the surfactant Cremophore EL improved yields. Triplet quantum yields ranged from 0.52 to 0.70 and fluorescence quantum yields ranged from <0.01 to 0.21. The nature of substituent (sulfonate, carboxy and pyridiloxy) did not influence photophysical properties. Chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine and its quaternised derivative displayed longer triplet lifetime than both the tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydroxy gallium octacarboxy phthalocyanine in DMSO and in aq. media in both the presence and absence of surfactant

New soluble methylendioxy-phenoxy-substituted zinc phthalocyanine derivatives : synthesis, photophysical and photochemical studies

The syntheses of new three phthalonitriles (1, 2 and 3), together with photophysical and photochemical properties of the resulting peripherally and non-peripherally tetrakis- and octakis 3,4-(methylendioxy)-phenoxy-substituted zinc phthalocyanines (4, 5 and 6) are described for the first time. Complexes 4, 5 and 6 have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. Complexes 4, 5 and 6 have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are mainly not aggregated (except for complex 6 in DMSO) within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO and toluene. Complex 4 has higher singlet oxygen quantum yields, fluorescence quantum yields, triplet quantum yields and triplet life times than complexes 5 and 6. The effect of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (4, 5 and 6) are also reported

Effects of ring substituents on electrocatalytic activity of manganese phthalocyanines towards the reduction of molecular oxygen

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

Photoinactivation of Candida albicans and Escherichia coli using aluminium phthalocyanine on gold nanoparticles

The conjugates of aluminium phthalocyanine (complex 1) with gold nanorods (complex 1–AuNRs) and bipyramids (complex 1–AuBPs) showed improved singlet oxygen quantum yields of 0.23 and 0.24, respectively, compared to that of complex 1 alone at 0.12. Complex 1 and its conjugates were used for the photoinactivation of fungi (C. albicans) and bacteria cells (E. coli). The Q band absorbances were the same for the Pc alone and when conjugated to AuNPs. The efficiency of these conjugates was evaluated by measuring the log reduction of the microorganisms (C. albicans and E. coli) after irradiation with visible light in the presence of photosensitizers. Aluminium phthalocyanine alone showed log 1.78 and log 2.51 reductions for C. albicans and E. coli respectively. However, the conjugates showed higher photosensitization with log 2.08 and log 3.34 for C. albicans and E. coli, respectively using 1–AuBPs. For complex 1–AuNRs log 2.53 and log 3.71 were achieved for C. albicans and E. coli respectively. The statistical analysis of the results showed that the enhanced photoinactivation observed in both microorganisms was irrespective of the shape of the nanoparticles conjugated. Photoinactivation of C. albicans was less than that of E. coli even though a higher concentration of complex 1 or its conjugates was used in C. albicans.Original publication is available at http://dx.doi.org/10.1039/C4PP00315BArbortext Advanced Print Publisher 9.1.520/W UnicodeAcrobat Distiller 10.0.0 (Windows); modified using iTextSharp 5.5.1 �2000-2014 iText Group NV (AGPL-version); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version

Synthesis, spectroscopic and electrochemical properties of manganese, nickel and iron octakis-(2-diethylaminoethanethiol)-phthalocyanine

The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the MnIIIPc−2/MnIIPc−2 (E½ = −0.12 V versus Ag|AgCl) and MnIIPc−2/MnIIPc−3 (E½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the FeIIPc−2/FeIPc−2 (E½ = −0.35 V versus Ag|AgCl) and FeIPc−2/FeIPc−3 (E½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to FeIIIPc−2/FeIIPc−2 (E½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes

Novel amperometric glucose biosensor based on an ether-linked cobalt(II) phthalocyaninecobalt(II) tetraphenylporphyrin pentamer as a redox mediator

The development of cobalt(II) phthalocyanine–cobalt(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin), (CoPc–(CoTPP)[subscript 4]) pentamer as a novel redox mediator for amperometric enzyme electrode sensitive to glucose is described. A glassy carbon electrode (GCE) was first modified with the pentamer, then followed by the immobilization onto the GCE–CoPc–(CoTPP)[subscript 4] with glucose oxidase (GOx) through cross-linking with glutaraldehyde in the presence of bovine serum albumin (BSA) and Nafion® cation-exchange polymer. The proposed biosensor displayed good amperometric respose charateristics to glucose in pH 7.0 PBS solution; such as low overpotentials (+400 mV versus Ag|AgCl), very fast amperometric response time (~5 s), linear concentration range extended up to 11 mM, with 10 μM detection limit. The biosensor exhibited electrochemical Michaelis–Menten kinetics and showed an average apparent Michaelis–Menten constant (K′M) of 14.91 ± 0.46 mM over a storage period of 2 weeks