The photophysical studies of Pluronic F127/P123 micelle mixture system loaded with metal free and Zn 5, 10, 15, 20-tetrakis [4-(benzyloxy) phenyl] porphyrins
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188932 , vital:44799 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.02.018"
- Description: Binary mixtures of Pluronics are studied as drug nanocarriers in this work. H2 and Zn 5,10,15,20-tetrakis[4-(benzyloxy) phenyl] porphyrin were encapsulated onto binary micelle mixture of Pluronic F127/P123. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence quantum yield for H2TBnOPP (ΦF = 0.034) was higher than that of ZnTBnOPP (ΦF = 0.023) and decreased when ZnTBnOPP or H2TBnOPP when in the presence of Pluronic F127/P123 binary mixtures. The kq values were 2.8 × 108 and 3.7 × 108 M−1 s−1, for H2TBnOPP + Pluronic F127/P123 and ZnTBnOPP + Pluronic F127/P123 in water, respectively. The binding constants (Kb) were 1.58 × 105 M−1 and 1.02 × 105 M−1 for ZnTBnOPP + Pluronic F127/P123 and H2TBnOPP + Pluronic F127/P123, respectively.
- Full Text:
- Date Issued: 2017
Fluorescence behaviour of supramolecular hybrids containing graphene quantum dots and pyrene-derivatized phthalocyanines and porphyrins
- Authors: Achadu, Ojodomo John , Managa, Muthumuni , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188953 , vital:44801 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.10.029"
- Description: Novel pyrene-derivatized zinc and cobalt phthalocyanines (Pcs) and porphyrins (Ps) were immobilized on graphene quantum dots (GQDs) to form GQDs-Pcs and GQDs-Ps supramolecular hybrids via the π–π stacking interaction method. Spectroscopic evidence shows that the resultant hybrids were stable owing to the strong π–π stacking interaction between the GQDs and the respective Pcs and Ps, thus leading to the fabrication of interesting and functional supramolecular hybrids by taking advantage of the delocalized π electron systems of GQDs and the macrocycles. The conjugates showed increased fluorescence quantum yields for the Pcs/Ps, but decreased values for the GQDs in the conjugates. These novel hybrid materials could potentially be deployed for studies in both fundamental and applied perspectives due to the synergistic contributions resulting from the combination of their excellent electronic and optical properties.
- Full Text:
- Date Issued: 2017
Beyond benefit sharing: Place attachment and the importance of access to protected areas for surrounding communities
- Authors: Cundill, Georgina , Bezerra, Joana C , de Vos, Alta , Ntingana, Nokuthula
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416265 , vital:71334 , xlink:href="https://doi.org/10.1016/j.ecoser.2017.03.011"
- Description: The concept of place attachment can assist to integrate relational values into ecosystem service research, and assist us to rethink the notion of benefits in contemporary protected area thinking. We present a case study from South Africa, where the concept of two-dimensional place attachment was used to understand the relationship between a protected area and a land claimant community that now owns part of this protected area but does not have physical access to the land. A place attachment lens helps refocus access to protected areas as cornerstone to long term sustainability of such areas. Such access must be considered in the context of spatially and economically differentiated users, including a focus on trade-offs between such users. Our findings highlight that when communities previously displaced from protected areas respond to offers of ‘benefit sharing’ with demands for access and recognition as land owners, they are asking for a recognition of relational values, and identity, based on close interaction with nature. A place attachment and relational values perspective raises questions about the extent to which traditional conservation practice can accommodate such values, and therefore meet local people’s expectations and remain viable in the long term.
- Full Text:
- Date Issued: 2017
Improved nonlinear optical behaviour of ball type indium (III) phthalocyanine linked to glutathione capped nanoparticles
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
Effects of symmetry and the number of positive charges on the photocatalytic activity of indium phthalocyanines when embedded in electrospun fibers
- Authors: Chakona, Gamuchirai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188304 , vital:44743 , xlink:href="https://doi.org/10.1016/j.ica.2016.12.025"
- Description: Photooxidations of bisphenol A and 4-chlorophenol were carried out in this study using two asymmetric indium(III) phthalocyanines photosensitizers: the first consisting of one quaternized 4-pyridyloxyl and no other substituents (complex 1) and the second containing three quaternized 4-pyridylsulfanyl units and one aminophenoxy (complex 3). The asymmetry of complex 3 is additionally caused by the presence of two linking atoms (O and S). The symmetrically substituted indium(III) phthalocyanine containing four quaternized 4-pyridyloxyl units (complex 2) was also studied. The complexes were embedded in electrospun polystyrene fiber for heterogeneous photocatalytic transformation of 4-chlorophenol and bisphenol A. When immobilized on electrospun fibers, complexes 1, 2 and 3 gave singlet oxygen values of 0.31, 0.39 and 0.50 in water, respectively. Complex 3 showed the best photocatalytic behavior with observed rate constants of 2.8 × 10−3 min−1 for bisphenol A and 3.8 × 10−3 min−1 for 4-chlorophenol.
- Full Text:
- Date Issued: 2017
Highly efficient CCl bond cleavage and unprecedented CC bond cleavage of environmentally toxic DDT through molecular electrochemical catalysis
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
- Date Issued: 2017
Photophysical behavior and photodynamic therapy activity of conjugates of zinc monocarboxyphenoxy phthalocyanine with human serum albumin and chitosan
- Authors: Oluwole, David O , Prinsloo, Earl , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188497 , vital:44759 , xlink:href="https://doi.org/10.1016/j.saa.2016.09.032"
- Description: Zincmonocarboxyphenoxy phthalocyanine (ZnMCPPc) was linked to human serum albumin (HSA) and chitosan via amide bond formation. The photophysical behavior and photodynamic therapy (PDT) activity (against human breast adenocarcinoma cell line (MCF-7 cells) of ZnMCPPc alone and its conjugates were investigated. The conjugates showed improved fluorescence, triplet and singlet oxygen quantum yields when compared to ZnMCPPc alone. The in vitro dark cytotoxicity and PDT studies were carried out at a dose of 3.6 μg/mL to 57.1 μg/mL. The in vitro dark cytotoxicity studies of ZnMCPPc showed cell viability more than 50% at 28.6 μg/mL and 57.1 μg/mL, while the conjugates showed > 50% in all their tested concentrations (3.6 to 57.1) μg/mL. Thus, conjugation of ZnMCPPc to HSA and chitosan improves its dark cytotoxicity, an important criteria for molecules meant for photodynamic therapy. Complex 1 showed the most efficacious PDT activity with cell viability more than 50% at concentration range of (14.3 to 57.1) μg/mL in comparison to the conjugates which only showed more than 50% cell viability at 28.6 μg/mL and 57.1 μg/mL for 1-HSA and 57.1 μg/mL for 1-Chitosan.
- Full Text:
- Date Issued: 2017
Investigation of photophysicochemical properties of zinc phthalocyanines conjugated to metallic nanoparticles
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
- Full Text:
- Date Issued: 2017
Exploiting Click Chemistry for the Covalent Immobilization of Tetra (4-Propargyloxyphenoxy) Metallophthalocyanines onto Phenylazide-Grafted Gold Surfaces
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
- Full Text:
- Date Issued: 2017
A2B type copper (III) corroles containing zero-to-five fluorine atoms
- Authors: Li, Minzhi , Niu, Yingjie , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238275 , vital:50604 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.10.044"
- Description: Four low symmetric A2B meso-substituted Cu(III)corroles with electron withdrawing meso-aryl rings have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to a series of DFT and TD-DFT calculations. A series of experiments demonstrate that these Cu(III)corroles can be used as highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, when the number of fluorine atoms at B meso-position is increased, there is a marked enhancement in the catalytic ability of the corrole complexes, which demonstrates that modification to the structures of low symmetry corroles is a useful strategy for developing new HER catalysts.
- Full Text:
- Date Issued: 2017
Photophysical properties of GaCl 5, 10, 15, 20-tetra (1-pyrenyl) porphyrinato incorporated into Pluronic F127 micelle
- Authors: Managa, Muthumuni , Britton, Jonathan , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233101 , vital:50056 , xlink:href="https://doi.org/10.1016/j.jlumin.2016.12.043"
- Description: GaCl 5,10,15,20-Tetra(1-pyrenyl)porphyrin (GaClTPyP) was successfully synthesised and encapsulated into Pluronic F127. The unmetallated 5,10,15,20-tetra(1-pyrenyl)porphyrin (H2TPyP) precursor was also encapsulated into Pluronic F127. The fluorescence quantum yield for GaClTPyP at 0.045 was lower than that of H2TPyP at 0.13 due to the heavy atom effect of Ga in the former which encourages intersystem crossing to the triplet state, lowering the fluorescence. Fluorescence quantum yield values increased when GaClTPyP or H2TPyP were encapsulated in Pluronic F127. GaClTPyP/Pluronic F127 showed higher values of the binding constant (Kb) as well as Stern-Volmer constant (Ksv) when compared to H2ClTPyP/Pluronic F127. It was determined from fluorescence quenching studies for GaClTPyP was located more in the inner core (hydrophobic) of Pluronic F127 and H2TPyP more on the outer region. Single oxygen quantum yields (Ф△) were determined to be 0.32 and 0.53 for GaClTPyP and GaClTPyP/Pluronic F127 respectively, an increase for the latter compared to the former.
- Full Text:
- Date Issued: 2017
Nonlinear optical dynamics of benzothiazole derivatized phthalocyanines in solution, thin films and when conjugated to nanoparticles
- Authors: Nwaji, Njemuwa , Jones, Benjamin , Mack, John , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190426 , vital:44993 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.05.042"
- Description: Benzothiazole phthalocynines complexes: tetrakis[(benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] indium(III) chloride (1) and tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] indium(III) chloride (2) were synthesisized and their nanosecond nonlinear optical behaviours in solution, solid state and when conjugated to metallic nanoparticles were examined and compared to those of the corresponding ZnPc and GaPc which are designated as: tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] zinc(II) (3), tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] gallium(III) chloride (4), tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] zinc(II) (5) and tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] gallium(III) chloride (6). Trends in the electronic structures were identified through a comparison of the UV–vis absorption and magnetic circular dichroism (MCD) spectroscopy of the complexes and calculated spectra predicted by time dependent density functional theory (TD-DFT). Of all the complexes and nanoconjugates, complex 2 (containing sulphur linkages and In as a central metal) gave the best optical limiting behaviour.
- Full Text:
- Date Issued: 2017
Azide-derivatized gold nanosphere “clicked” to indium and zinc phthalocyanines for improved nonlinear optical limiting
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188249 , vital:44738 , xlink:href="https://doi.org/10.1016/j.molstruc.2017.01.088"
- Description: We report on the conjugation of azide-derivatized gold nanoparticles (AuNPs) to alkyne moieties of ZnPc and InPc via azide-alkyne Huisgen cycloaddition reaction to form phthalocyanines-AuNPs (MPc-AuNPs) conjugates. The detailed structural characterizations of the composites were in good agreement with the expected results. The nonlinear absorption coefficients and other nonlinear optical limiting parameters were almost two times larger for the conjugates compared to free phthalocyanines. We established direct relationship between improved photophysical characterizations and enhanced nonlinear effects of reverse saturable absorption mechanisms favoured by excited triplet absorption of the phthalocyanines in the presence of AuNPs. The combination of InPc with AuNPs resulted in the lowest limiting intensity value of 0.06 J/cm2, hence the best performance in terms of optical limiting.
- Full Text:
- Date Issued: 2017
Electrocatalytic application for gold nanoparticles decorated sulfur-nitrogen co-doped graphene oxide nanosheets and nanosized cobalt tetra aminophenoxy phthalocyanine conjugates
- Authors: Shumba, Munyaradzi S , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188260 , vital:44739 , xlink:href="https://doi.org/10.1016/j.electacta.2017.03.154"
- Description: Sulfur and nitrogen affinity for gold is utilized to self-assemble gold nanorods (AuNRs) on S, N doped or S/N co-doped graphene oxide nanosheets (SGONS/AuNRs, NGONS/AuNRs or SNGONS/AuNRs) for enhancement of the electrocatalytic activity of nanosized cobalt tetra aminophenoxy phthalocyanine (complex 1) towards hydrogen peroxide detection. Of the electrodes containing AuNRs, 1-SNGONS/AuNRs-GCE gave the lowest limits of detection (LOD) of 0.012 μM followed by 1-SGONS/AuNRs-GCE and 1-AuNRs-SNGONS(seq)-GCE both with LOD of 0.016 μM. This work shows that in the absence of GONS (when AuNRs are alone and in the presence of 1 in 1/AuNRs-GCE), unfavorable detection limits are obtained and that doping of GONS is important in improving LOD. 1-SNGONS/AuNRs-GCE showed concentration dependent mechanisms resulting in two adsorption Gibbs energies (ΔGo) of −18.55 kJ mol−1 and −17.35 kJ mol−1 at high and low concentrations, respectively.
- Full Text:
- Date Issued: 2017
Effects of charge on the photophysicochemical properties of zinc phthalocyanine derivatives doped onto silica nanoparticles
- Authors: Peteni, Siwaphiwe , Sekhosana, Kutloano E , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188159 , vital:44728 , xlink:href="https://doi.org/10.1016/j.poly.2017.09.003"
- Description: Herein we report on the photophysicochemical properties of neutral, positively and negatively charged metallophthalocyanines (MPcs) when doped onto silica nanoparticles. The MPcs are: unsubstituted ZnPc (complex 1, neutral), Zn tetraaminophenoxy phthalocyanine (ZnTAPhPc, complex 2, neutral), tetrakis[4-(iodo-N-methylpyridinium)thio] phthalocyanine (ZnTMPyPc, complex 3, cationic), and Zn tetra sulfophenoxy phthalocyanine (ZnTSPhPc, complex 4, anionic). Following doping onto SiNPs, the triplet quantum yields increased for neutral complex 1 and positively charged complex 3. However, singlet oxygen quantum yields increased for positively charged 3 (in 3-SiNPs) and the negatively charge 4 (in 4-SiNPs) and not for complex 1 (in 1-SiNPs), compared to Pcs alone, due to the screening effect.
- Full Text:
- Date Issued: 2017
Nanosecond optical nonlinearities in low symmetry phthalocyanine nanoconjugates studied using the Z-scan technique
- Authors: Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188172 , vital:44729 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.08.053"
- Description: In this study, the photophysical, and nonlinear optical limiting properties of low symmetry tris[(4-benzo[d] thiazol-2-ylphenoxy)-2-phenoxyl acetic acid phthalocyaninato] zinc (II) (3) conjugated to metallic nanoparticles have been investigated using open aperture Z-scan techniques at 532 nm. The nonlinear optical response demonstrated that the studied complex and the nanoconjugates exhibits higher excited state absorption cross-section resulting from S1 and T1 compared to ground state absorption. Enhanced optical limiting performance was observed when the complex was conjugated to nanoparticles with 3SA-AuNPs showing the best optical limiting threshold of 0.39 J/cm2.
- Full Text:
- Date Issued: 2017
The effect of point of substitution and silver based nanoparticles on the photophysical and optical nonlinearity of indium carboxyphenoxy phthalocyanine
- Authors: Oluwole, David O , Ngxeke, Sixolisile M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188596 , vital:44768 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.07.032"
- Description: Indium(III) chloride 1,8(11),15(18),22(25)-tetra-(3-carboxyphenoxy) phthalocyanine (1) and indium(III) chloride 2,9(10),16(17),23(24)-tetra–(3-carboxyphenoxy) phthalocyanine (2) were covalently linked to glutathione capped silver nanoparticles (AgNPs–GSH) and silver selenide/zinc sulfide (Ag2Se/ZnS–GSH) quantum dots via amide bond formation. The photophysical and nonlinear optical behaviour of the metallophthalocyanines and their conjugates with nanoparticles were investigated using the open aperture Z–scan technique. Complex 2 showed enhanced photophysical properties compared to 1. The conjugates revealed improved triplet state quantum yields (except for 1-AgNPs-GSH which afforded lower triplet state quantum yields in comparison to 1) and nonlinear optical activities in comparison to the Pc complexes. The synthesized complexes, nanoparticles and their conjugates could be potential nonlinear optical materials due to their good nonlinear optical activities.
- Full Text:
- Date Issued: 2017
Understanding spatial variation in the drivers of nature-based tourism and their influence on the sustainability of private land conservation
- Authors: Baum, Julia , Cumming, Graeme S , de Vos, Alta
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416481 , vital:71352 , xlink:href="https://doi.org/10.1016/j.ecolecon.2017.05.005"
- Description: Protected areas connect socio-economic and ecological systems through their provision of ecosystem goods and services. Analysis of ecosystem services allows the expression of ecological benefits in economic terms. However, cultural services, such as recreation opportunities, have proved difficult to quantify. An important challenge for the analysis of cultural services is to understand the geography of service provision in relation to both human and ecological system elements. We used data on visitation rates and measures of context, content, connectivity, and location for 64 private land conservation areas (PLCAs) to better understand geographic influences on cultural service provision. Visitation to PLCAs was influenced by a combination of ecological and socio-economic drivers. Variance partitioning analysis showed that ecology explained the largest proportion of overall variation in visitation rates (26%), followed by location (22%). In tests using generalized linear mixed models, individual factors that significantly explained visitation rates included the number of mammal species, the number of Big 5-species (ecological variables), the number of facilities provided (infrastructure) and average accommodation charges (affordability). Our analysis has important implications for the economic sustainability of PLCAs and more generally for understanding the relevance of spatial variation for analyses of cultural services.
- Full Text:
- Date Issued: 2017
Halogen substituted A2B type Co (III) triarylcorroles
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- Full Text:
- Date Issued: 2017
Characterization of conjugates of NaYF4
- Authors: Watkins, Zane , Uddin, Imran , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238132 , vital:50589 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.10.011"
- Description: NaYF4:Er/Yb/Gd upconversion nanoparticles (UCNP) capped with amino groups were covalently attached to chloro aluminium tetrasulphonated phthalocyanine (ClAlTSPc) and chloro aluminium tetracarboxy phthalocyanine (ClAlTCPc). The conjugates were characterized using different techniques such as infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). There was a decrease in the intensity of fluorescence emission spectra of the UCNPs at 658 nm in the presence of the phthalocyanines. This decrease indicates an energy transfer between the donor UCNP and conjugated accepting phthalocyanine (Pc), due to Förster resonance energy transfer (FRET). FRET efficiencies of 18% and 21% for ClAlTSPc and ClAlTCPc, respectively, were obtained. Oxygen generation by ClAlTSPc following FRET was proved.
- Full Text:
- Date Issued: 2017