Search

Coal fly ash (class F) was used as feedstock to extract silica for the indirect synthesis of BEA zeolite via a hydrothermal process. The extraction steps selectively retained major components of Si > Al > Na and eliminated the need for the addition of an extra silica source in the zeolite synthesis mixtures. The stability of BEA zeolite was studied in hot liquid phase at different exposure times (6, 12 and 24 h) and temperatures (150 and 200 °C). The structural changes in the framework of the treated zeolite was determined with X-ray diffraction, thermogravimetric analysis, N2 adsorption–desorption and 27Al and 29Si magic-angle spinning nuclear magnetic resonance. Structural degradation of the treated zeolite depended on prolonged exposure time and high temperature, reduced crystallinity and framework Si/Al ratio, the degree of desilication, and the presence of silanol defects. The relative crystallinity and changes in framework Si/Al ratio were shown to depend on the exposure time and temperature in hot liquid phase. With prolonged exposure time, the surface area and micropore volume decreased with an increase in the mesopore volume. The stability of BEA zeolite was influenced by the hydrolysis of Si-O-Si bonds (siloxane) through desilication which eventually caused the formation of structural defects at elevated treatment time and temperature, however, the crystal structure remained intact. Herein, the stability of fly ash based BEA zeolite in hot liquid shows its potential use as a catalyst for liquid phase reactions, considering the exposure time and temperature investigated.

The endemic South African red seaweed Plocamium maxillosum (Poiret) Lamouroux produces two unusual isomeric dichlorinated cyclohexenone monoterpenes, plaxenone A and B (1 and 2). The structures of the isolated compounds were determined from spectroscopic data and their absolute configuration was determined by comparison of the experimental and calculated ECD spectra. Compounds 1 and 2 inhibit the growth of MDA-MB-231 breast cancer cells.

Asymmetric Mg (II) or Al (III) phthalocyanine (containing a COOH group and 3-pyridylsulfanyl units) was conjugated via an amide bond to amino functionalized magnetic nanoparticle (AIMN) to form MgPc-AIMN or AlPc-AIMN conjugate, and characterized. The photophysicochemical behaviour of the phthalocyanine-AIMN conjugates was investigated and compared to the asymmetric Pcs and to the simple mixture of Pc with AIMNs without a chemical bond, (MPc-AIMN (mixed)). The directed covalent linkage of AIMNs to the asymmetrical metallopthalocyanines afforded improvements in the singlet oxygen (ФΔ) and triplet state quantum yield (ФT) as well as singlet oxygen lifetimes for the MPcs-AIMN-linked conjugates compared to MPc-AIMN (mixed) and MPcs alone. The asymmetric phthalocyanines and their conjugates showed effective antimicrobial activity against Escherichia coli bacteria under illumination.

Light-assisted in vivo synthesis of gold nanoparticles (NPs) from aqueous solutions of dilute AuIII salts by a living green marine seaweed (Ulva armoricana) is reported for the first time. NPs synthesised using typical procedures have many associated environmental hazards. The reported methods involve green, nontoxic, eco-friendly synthetic procedures. The formation of AuNPs was extremely rapid (≈15 min) following illumination of the living U. armoricana, while the rate of NP formation in the dark was very slow (over 2 weeks). The properties of the AuNPs formed were confirmed using a battery of spectroscopic techniques. U. armoricana were found to be very efficient in Au0 uptake, and this, together with the rapid formation of AuNPs under illumination, indicated that the seaweed remained living during NP formation. The TEM images supported this, revealing that the thylakoid membranes and cell structure remained intact. The AuNPs formed on the surface of U. armoricana thallus, along the cell walls and in the chloroplasts. Without further workup, the dried, U. armoricana-supported AuNPs were efficient in the catalytic reduction of 4-nitrophenol, demonstrating the completely green cycle of AuNP formation and catalytic activity. The results mean that an aquatic plant growing in water rich in gold salts could bio-accumulate AuNPs from its aquatic environment, simply with the activation of sunlight.

Marine sponges – in common with many other sessile marine invertebrates seemingly devoid of obvious physical forms of defence against predators, e.g. spines or shells – are the sources of a diverse array of organic chemical compounds known as marine natural products or secondary metabolites. Recent research has indicated that the production of natural products via cellular secondary metabolic pathways in some sponge species may not occur within the sponge cells themselves, but rather in microbial endosymbionts which inhabit the surface and interstitial spaces within the sponge tissue. Regardless of their biosynthetic origin, the bioactivity, e.g. toxicity, of many of these marine natural products may be utilised by sponges as chemical feeding deterrents to discourage predation or to provide a chemical anti-fouling competitive edge in the intense competition for living space amongst filter-feeders on space-limited benthic reefs. Paradoxically, a small number of sponge natural products have serendipitously shown potential as new pharmaceuticals, e.g. novel anti-cancer drugs. Marine biodiscovery (or bioprospecting) is the search for new pharmaceuticals from marine organisms. Exploration of the taxonomy, natural products chemistry and biomedicinal potential of the rich diversity of South African latrunculid sponges (family Latrunculiidae), at Rhodes University, the South African Department of Environmental Affairs and the University of the Western Cape has continued unabated for over a quarter of a century as part of a collaborative marine biodiscovery programme. A short review of this multidisciplinary latrunculid sponge research is presented here.

This paper reports on the synthesis of single walled carbon nanotubes (SWCNTs) from an activated mixture of iron (II) phthalocyanine, its metal-free derivative and ferric acetate. The powdered mixture was activated by compression into a tablet by applying a force of 300 kN, followed by re-grinding into powder and heating it to high temperatures (1000°C). The activation by compression resulted in more than 50% debundling of SWCNTs as judged by transition electron microscopy. Acid functionalization of the SWCNTs was confirmed by the increase in the D:G ratio from 0.56 to 0.87 in the Raman spectra and the observation of an average of one carboxylic acid group per 13 carbon atoms from thermogravimetric analysis (TGA). TGA also showed that the initial decomposition temperatures for the activated and non-activated mixtures to be 205°C and 245°C, respectively. Hence, activation leads to the lowering of the pyrolysis temperature of the phthalocyanines. X-ray diffraction, electronic absorption and Fourier transform infrared spectra were also employed to characterize the SWCNT.

Zinc tetracarboxyphenoxy phthalocyanine was covalently linked to Gd 2 O 3 nanoparticles for the photocatalytic degradation of Orange G. Characterization of the composite was carried out using XRD, TEM, XPS, UV–vis spectroscopy and FT-IR spectroscopy. The composite showed improved photophysical properties over the phthalocyanine alone and the catalyst was found to be reusable. Analyses of the photodegradation rates of the azo dye indicated pseudo first-order kinetics.

Magnetite nanoparticles (MNPs) were synthesised by the co-precipitation method and coated with amino functional groups which allowed for amide bond formation with the carboxylic acid groups on zinc tetra- or octa-carboxyphthalocyanine (ZnTCPc or ZnOCPc respectively). The absorption spectra of ZnTCPc linked to MNPs showed a reduction in aggregation, while the photophysical parameters (Φ(T), τ(T) and Φ(Δ) of ZnTCPc or ZnOCPc increased upon linking with the MNPs.

Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine's Q band, which was accompanied by a decrease in the Pc's fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle's and phthalocyanine's emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd(3+) ions).

Light-assisted in vivo synthesis of gold nanoparticles (NPs) from aqueous solutions of dilute Au

Functionalised electrospun polyamide-6 (PA-6) nanofibres incorporating gadolinium oxide nanoparticles conjugated to zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) as the sensitizer were prepared for the photocatalytic degradation of Orange G. Fibres incorporating the phthalocyanine alone or a mixture of the nanoparticles and phthalocyanine were also generated. The singlet oxygen-generating ability of the sensitizer was shown to be maintained within the fibre mat, with the singlet oxygen quantum yields increasing upon incorporation of the magnetic nanoparticles. Consequently, the rate of the photodegradation of Orange G was observed to increase with an increase in singlet oxygen quantum yield. A reduction in the half-lives for the functionalised nanofibres was recorded in the presence of the magnetic nanoparticles, indicating an improvement in the efficiency of the degradation process.

The use of natural products as chemotherapeutic agents is well established, however, many of these are associated with undesirable side effects, including high toxicity and instability. Furthermore, the development of drug resistant cancers makes the search for new anticancer lead compounds a priority. In this study, the extraction of an Ircinia sp. sponge resulted in the isolation of an inseparable mixture of (7E,12E,20Z)-variabilin (1) and (7E,12Z,20Z)-variabilin (2) and structural assignment was established using standard 1D and 2D NMR experiments. The cytotoxic activity of the compound against three solid tumour cell lines displayed moderate anti-cancer activity through apoptosis, together with a general lack of selectivity among the cancer cell lines studied. Structural assignment and cytotoxic evaluation of variabilin was complicated and further aggravated by its inherent instability. Variabilin was therefore incorporated into solid lipid nanoparticles (SLNs) and the stability and cytotoxic activity evaluated. Encapsulation of variabilin into SLNs led to a marked improvement in stability of the natural product coupled with enhanced cytotoxic activity, particularly against the prostate (PC-3) cancer cell line, with IC50 values of 87.74 &mu, M vs. 8.94 &mu, M for the variabilin alone and Var-SLN, respectively. Both variabilin and Var-SLN revealed comparable activity to Ceramide against the MCF-7 breast cancer cell line, revealing IC50 values of 34.8, 38.1 and 33.6 &mu, M for variabilin, Var-SLN and Ceramide, respectively. These samples revealed no activity (&gt, 100 &mu, M for all) against HT-29 (colon) cell lines and MCF-12 (normal breast) cell lines. Var-SLNs induced 47, 48 and 59% of apoptosis in HT-29, MCF-7 and PC-3 cells, respectively, while variabilin alone revealed 38, 29 and 29% apoptotic cells for HT-29, MCF-7 and PC-3 cell lines, respectively. The encapsulation of natural products into SLNs may provide a promising approach to overcome some of the issues hindering the development of new anticancer drugs from natural products.

The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of p...

This work reports on the grafting of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally and peripherally with a 4-amino phenoxy group. The phthalocyanine dyes have free amino groups, facilitating covalent attachment of the dyes on the silica surface via amide bond formation. The surface area of the functionalized silica nanoparticles increased on conjugation but the pore volumes were reduced. The phthalocyanine functionalized silica nanoparticles showed lower fluorescence quantum yields as well as shorter triplet lifetimes compared to the free phthalocyanines in dimethyl formamide. For the non-peripherally substituted phthalocyanines increases in triplet yield quantum yields, lifetimes, and singlet oxygen quantum yields were observed.

In this study, we report on the covalent linking of carboxylic acid functionalized silica nanoparticles with zinc phthalocyanine mono-substituted non-peripherally and peripherally with either a 4-amino phenoxy (1, peripheral and 2, non-peripheral) or an amino group (3 peripheral). The grafting is achieved via the formation of an amide bond between the carboxylic acid of the silica nanoparticles and the amino group of the phthalocyanine complexes. The hybrid nanoparticles retained the amorphous nature of silica nanoparticles after conjugation. A slight decrease in fluorescence and a general improvement in triplet quantum yields compared to free Pcs were observed. Triplet lifetimes for 2- SiNPs and 3- SiNPs also improved when compared to the free phthalocyanine. The changes in singlet oxygen quantum yields upon conjugation were minimal.

Platination of dihydroxosilicon octacarboxyphthalocyanine (OH)2SiOCPc was successfully carried out to give dihydroxosilicon tris(diaquaplatinum)octacarboxyphthalocyanine (OH)2SiOCPc(Pt)3 conjugate. Slight blue shifting of the absorption spectrum of (OH)2SiOCPc(Pt)3 was observed on conjugation with platinum. Comparative photophysicochemical behavior and antimicrobial photo-activities of (OH)2SiOCPc(Pt)3 conjugate with (OH)2SiOCPc or Pt nanoparticles revealed that the heavy atom, Pt on the periphery of the phthalocyanine significantly enhanced its singlet oxygen generation with a quantum yield of 0.56 obtained for the (OH)2SiOCPc(Pt)3 conjugate. The (OH)2SiOCPc(Pt)3 conjugate showed highest antimicrobial activity towards Candida albicans and Escherichia coli compared to (OH)2SiOCPc and Pt nanoparticles alone under illumination.

The synthesis of a zinc phthalocyanine complex tetrasubstituted with carbazole functionality at the peripheral position (complex 4) is reported. The singlet oxygen quantum yield of the complex was found to be 0.83 in dimethylformamide (DMF). The complex was subsequently conjugated to zinc oxide microparticles (ZnOMPs), the conjugation (formation of the amide bond) was confirmed by IR spectroscopy. The presence of ZnOMPs was found to reduce the singlet oxygen produced (ΦΔ = 0.63) in DMF. Polystyrene electrospun fibers of complex 4 alone and its conjugate to ZnOMPs were found to be thermally stable. The singlet oxygen quantum yield of the modified electrospun fibers was determined in aqueous media with ADMA as a singlet oxygen quencher and were 0.25 and 0.20 for complex 4 and 4-ZnOMPs embedded in fibers, respectively.

We report on the electrodeposition of gold nanoparticles (AuNPs) onto the glassy carbon electrode (GCE) followed by polymerization of cobalt tetraamino phthalocyanine (CoPc(NH 2 ) 4 ) on top (represented as poly-CoPc(NH 2 ) 4 -/AuNPs-GCE). The modified electrode where CoPc(NH 2 ) 4 is polymerized first followed by deposition of AuNPs is represented as AuNPs/poly-CoPc(NH 2 ) 4 -GCE. In the absence of AuNPs, the electrode is represented as poly-CoPc(NH 2 ) 4 -GCE or for AuNPs alone (AuNPs-GCE). The surface coverage was 1.5 × 10 −9 mol cm −2 for AuNPs-GCE and 3.0 × 10 −9 mol cm −2 for the rest of the modified electrodes. AuNPs/CoPc(NH 2 ) 4 -GCE exhibited high electrocatalytic activity towards the oxidation of nitrite, with detection potential of 0.76 V. The catalytic rate constant of 3.96 × 10 7 cm 3 mol −1 s −1 was obtained for nitrite oxidation.

A chelating ion exchanger, prepared by functionalising Merrifield resin with 2,2′-pyridylimidazole, was utilized to selectively adsorb and separate nickel from other base metal ions in synthetic sulfate solutions. The sorbent material was characterized by scanning electron microscopy (SEM), microanalysis, infrared (IR), X-ray photoelectron spectroscopy (XPS) and BET surface area. The distribution ratio (D) and the sorption capacity of the microspheres toward Ni(II), Cu(II), Co(II) and Fe(II) ions was studied by using the batch and column methods, respectively. Ni(II) followed by Cu(II) showed the highest distribution ratio (D) and the highest sorption efficiency of nickel(II) ions around pH 2. The binary separation of nickel(II) from copper(II), cobalt(II) and iron(II) respectively, undertaken in a column study, through loading the metal ions at pH ≈ 2 followed by selective decomplexation, demonstrated the selectivity of the sorbent material for nickel(II). Thus, 2,2′-pyridylimidazole can be regarded as a nickel-specific extractant.

Zinc octacarboxy phthalocyanine (ZnOCPc) was covalently immobilized on the surface of magnetite nanoparticles (MNPs) for the photocatalytic degradation of Orange G (OG) under visible light irradiation. It is noteworthy that the catalyst can be easily recovered using an external magnet and that it is reusable. The ZnOCPc remained bound to the MNP surface even after 25 min of photolysis as confirmed by the FT-IR and X-ray diffraction spectra. Kinetic analysis shows that the photodegradation rates of OG can be approximated to be pseudo-first order, according to the Langmuir–Hinshelwood kinetics model.

In this work, we investigated the nonlinear optical absorption properties of chloroaluminum, chlorogallium, chloroindium, zinc and lead octaphenoxy phthalocyanines in a dimethyl sulphoxide solution using 5 ns pulses at 532 nm. Using the Z-scan technique, the nonlinear optical properties and the excited state absorption cross-sections were determined by fitting the Z-scan data. The k value was the highest for Pb derivative at 211, making it the best nonlinear optical material. In terms of hyperpolarizability, Pb derivative (containing a larger central metal) also gave the largest value followed by aluminum derivative (containing a small central metal). The distortion of the ring caused by the central metal is used to explain the hyperpolarizability values. Large nonlinear absorption coefficient values, β eff , in the range of 3.558–4.763 × 10-9 cm.W-1 and low saturation fluence values, F sat between 21.5–38.5 mJ.cm-2, were obtained for these samples.

3(4),15(16)-Bis-(4- tert- butyl-phenoxy)-10,22-diaminohemiporphyrazinato chloroindium hemiporphyrazine was synthesized from 1,3,5-triaminobenzene and 4-tert-butyl-phenoxyisoindoline. The structure of the complex was confirmed using mass, nuclear magnetic resonance and infrared spectroscopies. The nonlinear parameters of the compound was also analyzed in dimethylformamide and found to be significantly greater than previously analyzed phthalocyanines.

The synthesis of new zinc phthalocyanine complexes containing 3-(2-benzothiazol-2-yloxy) (complex 3) and 3-(carbazol-2-yloxy) (complex 4) substituents at the non-peripheral positions are reported. The new compounds were characterized by elemental analysis, FT-IR, 1H NMR, mass spectrometry and UV–Vis spectroscopy. The effects of carbazole and benzothiazole substitutents on the photophysical and photochemical parameters of ZnPc are reported. These new phthalocyanines are non-aggregated in common solvents and show improved photophysicochemical properties. The 3-(2-benzothiazol-2-yloxy) substituted complex showed the longest triplet lifetime ever reported for a zinc phthalocyanine (1.7 ms).

This study reports on the photophysical and photochemical behavior of the conjugates formed by covalent and non-covalent bonding between zinc monoamino phthalocyanine (ZnMAPc) and either single walled carbon nanotubes (SWCNTs) or folic acid (FA). The conjugates were characterized using FTIR, X-ray powder diffractometry, thermogravimetric analyses, transmission electron microscopy and Raman spectroscopy. 1 H NMR and mass spectroscopies were only employed for ZnMAPc–FA conjugate. There was a slight increase in the triplet and singlet oxygen quantum yields on conjugating ZnMAPc to SWCNTs (or FA), while a decrease in the photophysical and photochemical parameters were observed upon adsorption of the ZnMAPc–FA conjugate to SWCNTs.

This review presents recent data on the photophysical behavior of phthalocyanines when conjugated to quantum dots, gold and magnetic nanoparticles. In some cases such conjugates offer the possibility of being used in “combination therapy”, where two or more substances may be used for treating one disease. The review focuses on the effect that the presence of nanoparticles has on the excited and triplet state parameters of the phthalocyanines. Five tables listing these parameters are presented.

The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting V IV OSO 4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V 4+ ) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m 2 g −1 and porosity of 135 A, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert -butyl hydroperoxide ( t -BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher ( t -BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.

We report on the synthesis of Ni nanoparticles (NiNPs) and their application in electrocatalysis in comparison with nickel phthalocyanine (NiPc). UV–vis spectroscopy, powder X-ray diffraction, transmission electron microscopy and electron paramagnetic resonance were used in the characterization of NiNPs. Cyclic voltammetry and electrochemical impedance spectroscopy were used in electrocatalytic studies of amitrole on the glassy carbon electrode modified with NiNPs. The apparent and catalytic rate constants for amitrole on the NiNP-GCE were found to be 2.58 × 10−5 cm s−1 and 1.11 × 103 M−1 s−1, respectively.

This work reports on the axial coordination of zinc phthalocyanine and bis-(1,6-hexanedithiol) silicon phthalocyanine to silver and gold nanoparticles. Red shifting of absorption spectra of the phthalocyanine complexes was observed after conjugation with the nanoparticles. An improvement in the photophysicochemical behavior and antimicrobial activity was achieved in the presence of metal nanoparticles for both complexes. A decrease in triplet lifetimes was observed for all the phthalocyanine metal nanoparticle conjugates. The Zn phthalocyanine complex gave the highest triplet and singlet oxygen quantum yield in the presence of gold nanoparticles. On the other hand, the bacterial inhibition was found to be best for the Si phthalocyanine derivative in the presence of nanoparticles compared to the Zn phthalocyanine counterpart. The highest antimicrobial activity was achieved for both conjugates against B. subtilis compared to S. aureaus both in the dark and under illumination with light.

Hydroxy aluminium octacarboxy phthalocyanine (Al(OH)OCPc) was conjugated with a diammine platinum complex to give conjugates containing two or three platinum complexes (represented as: Al(OH)OCPc(Pt) 2 and Al(OH)OCPc(Pt) 3 ). It was found that the complexes were soluble in water at a pH > 8.2. Both conjugates were found to have two fluorescence lifetimes. The triplet and singlet oxygen quantum yields increased for the conjugates compared to Al(OH)OCPc alone.

The heterogeneous photocatalytic activity of Zn(II) phthalocyanine-gold nanoparticle conjugates immobilized on electrospun polystyrene fibers was investigated using 4-chlorophenol and Orange G as model pollutants. The phthalocyanine-gold nanoparticle conjugates were synthesized via a ligand exchange reaction and characterized using spectroscopic and microscopic techniques. The interaction between the gold nanoparticles and phthalocyanines did not restrict the formation of excited singlet states, triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and enhanced photocatalytic activity compared to the phthalocyanines. It was concluded that hybrid electrospun fibers provide great potential as active photocatalysts for oxidizing organic pollutants using singlet oxygen as an oxidant.

This work reports on the functionalization of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally with 4-carboxyphenoxyl and 3-carboxyphenoxyl groups. The phthalocyanine dyes have a free carboxyl group, facilitating the covalent attachment of the dyes on the silica surface via amide bond formation. The phthalocyanine functionalized silica nanoparticles showed higher fluorescence and triplet quantum yields as well as longer triplet lifetimes compared to the free phthalocyanines.

The covalent linking of thiol-capped CdTe@ZnS QDs with cobalt tetraamino-phthalocyanine (CoTAPc) has been successfully carried out. Several techniques such as time-resolved fluorescence measurements, thermal gravimetric analysis, transmission electron microscopy and spectrophotometric techniques were employed to characterize the nanoconjugates. Covalent binding of the QDs with CoTAPc resulted in the fluorescence quenching of the former. In the presence of varying concentrations of superoxide anion (O 2 − ), the fluorescence of the QDs in the conjugate was gradually enhanced and the detection limits obtained were 2.1 and 2.4 nM for the smaller and larger QDs, respectively. Based on the excellent selectivity displayed by the nanoconjugates towards O 2 − over other biologically active species, a potential nanosensor was developed.

Core–shell CdTe@ZnS quantum dots capped with glutathione (CdTe@ZnS–GSH) were covalently linked to zinc octacarboxy phthalocyanine (ZnPc(COOH) 8 ). The conjugate was characterized by UV/Vis, infrared and X-Ray photoelectron spectroscopies as well as transmission electron and atomic force microscopies. The fluorescence quantum yields of the core CdTe capped with thioglycolic acid increased upon formation of the core-shell. Upon conjugation with ZnPc(COOH) 8 , the fluorescence quantum yield of CdTe@ZnS–GSH decreased due to energy transfer from the latter to the Pc. The average fluorescence lifetime of the CdTe@ZnS–GSH QD also decreased upon conjugation from 26.2 to 13.3 ns.

Conjugates of zinc tetracarboxy phthalocyanine (ZnPc(COOH)4) with CdTe@ZnS–GSH quantum dots (QDs) were synthesized and characterized by several techniques including X-ray powder diffraction and infrared spectroscopy. There was an observed decrease in both the fluorescence quantum yields and lifetimes of the quantum dots when they were linked or mixed with ZnPc(COOH)4 due to Forster resonance energy transfer (FRET). The FRET behavior of CdTe@ZnS–GSH–ZnPc(COOH)4 conjugates was compared to that of CdTe@ZnS–GSH–ZnPc(COOH)8. Higher FRET efficiencies were observed for CdTe@ZnS–GSH–ZnPc(COOH)4-mixed or CdTe@ZnS–GSH–ZnPc(COOH)4-linked compared to the corresponding CdTe@ZnS–GSH–ZnPc(COOH)8-mixed or CdTe@ZnS–GSH–ZnPc(COOH)8-linked. Also CdTe@ZnS–GSH–ZnPc(COOH)4-mixed (containing coreshell QDs) showed higher FRET efficiency than CdTE–TGA–ZnPc(COOH)4-mixed containing core QDs. The FRET efficiencies were found to be 63% and 59% for the CdTe@ZnS–GSH–ZnPc(COOH)4-linked and CdTe@ZnS–GSH–ZnPc(COOH)4-mixed samples, respectively.

A variety of nanoparticles (NPs), including FePt nanoparticles with Fe as the shell (2) or Pt as the shell (3), Pt NPs (4), and FePd (5) were synthesised, characterised and their effect on a zinc phthalocyanine (1) tetra-substituted with a pyridyl-oxy substituent studied using UV/Vis and fluorescence spectroscopy (including time correlated single photon counting, TCSPC). The nanoparticles were characterised using a number of techniques including UV/Vis and inductively coupled plasma-optical emission (ICP-OES) spectroscopies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and electron paramagnetic resonance (EPR) spectroscopy. Nanocomposites (NCs, 6,7) where the ZnPc (1) was used as the stabiliser, instead of oleic acid and or oleylamine, were also synthesised and characterised.

This work reports on the synthesis of zinc tetraaminophthalocyanine (ZnTAPc) functionalized with folic acid (FA), forming ZnTAPcFA. The conjugate between FA and ZnTAPc was soluble in water whereas ZnTAPc alone is not. The structure of ZnTAPcFA conjugate was elucidated by 1H NMR, MALDI-TOF mass and FTIR spectra. Photophysical and photochemical studies of ZnTAPcFA were conducted in DMSO. The increase in fluorescence quantum yield of the conjugate was accompanied by a decrease in the triplet and singlet oxygen quantum yields. The changes in triplet quantum and singlet oxygen quantum yields were marginal when ZnTAPc was simply mixed with FA without a chemical bond.

Polymer composite fibers doped with phthalocyanines and phthalocyanine-functionalized gold nanoparticles were developed. The phthalocyanine and phthalocyanine-functionalized gold nanoparticles have been characterized using UV/Vis, fluorescence and X-ray photoelectron spectroscopy (XPS), time correlated single photon counting (TCSPC), time-resolved emission spectra (TRES) and transmission electron microscopy (TEM). The changes in photophysical and photochemical behavior of the phthalocyanines induced by their interaction with gold nanoparticles and polystyrene were also investigated. In the presence of gold nanoparticles, the fluorescence lifetimes and quantum yields of the phthalocyanine decreased, whereas the singlet oxygen quantum yield increased. This work shows that polymer composite fibers could be used as functional fibers for a variety of applications such as gas sensing when using the advantageous properties of phthalocyanines and gold nanoparticles.

A detailed, methodical approach was used to synthesise silver and gold nanoparticles using two differently prepared aqueous extracts of the brown algae Sargassum incisifolium. The efficiency of the extracts in producing nanoparticles were compared to commercially available brown algal fucoidans, a major constituent of brown algal aqueous extracts. The nanoparticles were characterised using TEM, XRD and UV/Vis spectroscopy and zeta potential measurements. The rate of nanoparticle formation was assessed using UV/Vis spectroscopy and related to the size, shape and morphology of the nanoparticles as revealed by TEM. The antioxidant, reducing power and total polyphenolic contents of the aqueous extracts and fucoidans were determined, revealing that the aqueous extracts with the highest contents produced smaller, spherical, more monodisperse nanoparticles at a faster rate. The nanoparticles were assessed against two gram-negative bacteria, two gram-positive bacteria and one yeast strain. In contrast to the literature, the silver nanoparticles produced using the aqueous extracts were particularly toxic to Gram-negative bacteria, while the gold nanoparticles lacked activity. The cytotoxic activity of the nanoparticles was also evaluated against cancerous (HT-29, MCF-7) and non-cancerous (MCF-12a) cell lines. The silver nanoparticles displayed selectivity, since the MCF-12a cell line was found to be resistant to the nanoparticles, while the cancerous HT-29 cell line was found to be sensitive (10% viability). The gold nanoparticles displayed negligible toxicity.

This work reports on the synthesis and the physicochemical properties of novel unsymmetrically substituted zinc phthalocyanines (complexes 8, 10 and 11) and their symmetrically substituted counterparts (complexes 9, 12 and 13). The new complexes and their counterparts were successfully structurally characterized by IR, NMR, mass spectral and elemental analyses. Low fluorescence quantum yields (0.032) and lifetimes (0.91 ns) were obtained for the symmetrical ZnOTPc (complex 9) compared to the higher fluorescence quantum yields (0.15, 0.13, 0.10, 0.09 and 0.29) and lifetimes (4.4, 1.69, 1.69, 2.16 and 3.23 ns) obtained for ZnMPCPc (8), ZnTDTPc (12), ZnMCapPc (10), ZnMCafPc (11) and ZnTCPPc (13), respectively. All the complexes showed the ability to produce singlet oxygen with the highest triplet quantum yields obtained for 8 and 10 (0.80 and 0.65 respectively). High triplet lifetimes (109–286 μs) were obtained for all complexes. Complex 8 showed the longest triplet and fluorescence lifetimes as well the largest triplet state and singlet oxygen quantum yields.

The combination of chemotherapy and photodynamic therapy was investigated by the synthesis and characterisation of phthalocyanine conjugates with Pt complexes. The complexes synthesized are: hydroxoaluminum trikis(diaquaplatinum) octacarboxyphthalocyanine (OHAlOCPc(Pt) 3 ) and hydroxoaluminum tetrakis(diaquaplatinum) octacarboxyphthalocyanine (OHAlOCPc(Pt) 4 ). The platinated phthalocyanine complexes gave long triplet lifetimes of 577 and 526 μs for OHAlOCPc(Pt) 3 and OHAlOCPc(Pt) 4 , respectively. The triplet quantum yields were found to be 0.45 for OHAlOCPc(Pt) 3 and 0.57 OHAlOCPc(Pt) 4 while the singlet oxygen quantum yields were found to be 0.38 and 0.48, respectively.

Zinc 2, (3)-tri-(phenylthio)-2, (3)-carboxy phthalocyanine (ZnPc(COOH)(SPh)3), zinc 2, (3)-tetra-(phenylthio) phthalocyanine (ZnPc(SPh)4) and 2, (3)-tetra-(phenylthio) phthalocyanine (H2Pc(SPh)4) were synthesized and their photophysical behavior were compared with those of a number of zinc phthalocyanine (ZnPc) derivatives. ZnPc(COOH)(SPh)3 and ZnPc(SPh)4 had similar fluorescence (ΦF=0.14) and triplet state (ΦT=0.65) quantum yields in dimethylsulfoxide, hence showing no effects of the replacement of one of the phenylthio groups with a carboxylic acid group. ZnPc(COOH)(SPh)3 displayed a slightly shorter triplet lifetime (τT=331 μs) than ZnPc (τT=350 μs) in DMSO, but within the range of ZnPc derivatives. The triplet lifetime for ZnPc(COOH)(SPh)3 is much longer than for the symmetrical derivative (ZnPc(SPh)4) with τT=149 μs in DMSO.

Aryl-derivatized ZnPc (tetrakis (benzylmercapto) zinc phthalocyanine, ZnTBMPc) was synthesized and used to functionalize gold nanoparticles (AuNPs) by ligand exchange. The triplet quantum yield and lifetime of ZnTBMPc were determined to be 0.51 and 50 μs and a singlet oxygen quantum yield ( Φ Δ ) of 0.33 was obtained in toluene. When conjugated to AuNPs, the Φ Δ value of 0.54 was obtained in toluene. Poly(methyl methacrylate) fiber was electrospun in the absence and presence of ZnTBMPc and its conjugate with AuNPs. The functionalized fiber showed an ability to generate singlet oxygen for both ZnTBMPc and its AuNPs conjugate. The functionalized phthalocyanine fiber could be a promising fabric material for applications as photosensitizers.

Magnesium and aluminium phthalocyanines tetrasubstituted with 2-(dimethylamino) ethanethiol have been synthesized (complexes 2 and 3). The prepared complexes were converted to water soluble ones by quaternizing with methyl iodide. The quaternized complexes (2Q, 3Q) show monomeric behaviour in organic solvents but show aggregation in water, especially for 2Q. Furthermore the water soluble complexes were conjugated with gold nanoparticles in DMSO to avoid aggregation of the phthalocyanines in water. The phthalocyanines showed a blue shift in their Q bands upon conjugation with gold nanoparticles. Low fluorescence quantum yields and lifetimes were also observed for the conjugates compared to the non-conjugated phthalocyanine molecules. The conjugated complexes showed an increase in the triplet quantum yields with a concomitant decrease in their triplet lifetimes.

This work reports on the photodynamic activity of Zn phthalocyanine-ɛ-polylysine conjugates in the presence of gold and silver nanoparticles (NPs) towards the inactivation of Staphylococcus aureus ( S. aureus ). The conjugates showed high photoinactivation with ∼6% growth at a drug dose of 3 μM and fluence of 39.6 mW/cm 2 for 10 min irradiation time in the presence of silver nanoparticles. The presence of silver nanoparticels from the minimal inhibition concentration (MIC 50 ) studies showed remarkable growth inhibition for the tested conjugates even at low concentrations. The MIC 50 was lowest for the conjugate of 3 with ɛ-polylysine at concentrations of less than 0.0058 μM in the presence of AgNPs. The lethal photosensitization of microorganisms has emerged as a promising treatment since bacteria have reduced possibilities of developing resistance to photodynamic therapy.

Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh) 4 ). The conjugates formed are represented as ZnPc(SPh) 4 –AuNP. The absorption spectrum of the ZnPc(SPh) 4 –AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).

An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.

The characterization of tantalum phthalocyanine conjugates with gold nanoparticles and single wall carbon nanotubes as well as their electrocatalytic oxidation of bisphenol A is hereby presented. The formation of the conjugates was confirmed by X-ray diffraction and transmission electron microscope techniques. Single walled carbon nanotube conjugates of TaPc complexes showed the best catalysis as well as less passivation for bisphenol A detection and significant recovery of ∼98% compared to gold nanoparticle conjugates.