Photophysical and redox properties of a series of phthalocyanines: relation with their photodynamic activities on TF-1 and Daudi leukemic cells

The photodynamic therapy (PDT) efficiency of five phthalocyanines, chloroaluminum phthalocyanine (AlPc), dichlorosilicon phthalocyanine (SiPc), bis(tri-n-hexylsiloxy)silicon phthalocyanine (PcHEX), bis(triphenylsiloxy)silicon phthalocyanine (PcPHE) and nickel phthalocyanine (NiPc), was assessed on two leukemic cell lines TF-1 and erythroleukemic and B lymphoblastic cell lines, Daudi, respectively. AlPc showed the best photocytotoxicity leading to 0.008 surviving fraction at 2 x 10(-9) M for TF-1 and 4 x 10(-9) M for Daudi. A1 5 x 10(-7) M, SiPc and PcHEX induced a significant photokilling, whereas NiPc and PcPHE were inactive. Laser flash photolysis and photoredox properties of the phthalocyanines were investigated to try to relate these parameters with the biological effects. AlPc showed the longest triplet life-time: 484 microseconds in dimethyl sulfoxide/H2O. This value was increased up to 820 microseconds when AlPc was complexed with human serum albumin used as a membrane model. Such an enhancement was not observed with the silicon phthalocyanines. Upon irradiation, all the phthalocyanines generated singlet oxygen with 0.29-0.37 quantum yield values. The reduction potentials of the excited states obtained from measurement in the ground state and energy of the excited triplets show that AlPc is the best electron acceptor. The in vitro photocytotoxicity observed and the measured parameters are in agreement with a key role of electron transfer in PDT assays involving these phthalocyanines.     

Bifunctional Perovskite-BiVO4 Tandem Devices for Uninterrupted Solar and Electrocatalytic Water Splitting Cycles

Photoelectrochemical (PEC) fuel synthesis depends on the intermittent solar intensity of the diurnal cycle and ceases at night. Here, an integrated device that does not only possess PEC water splitting functionality, but also operates as an electrolyzer in the nocturnal period to improve the overall capacity factor is described. The bifunctional system is based on an “artificial leaf” tandem PEC architecture that contains an inverse-structure lead halide perovskite protected by a graphite epoxy/parylene-C coating (conferring 96 h stability of operation in water), and a porous BiVO₄ semiconductor. The light-absorbers are interfaced with a H₂ evolution catalyst (Pt) and a Co-based water oxidation catalyst, respectively, which can also be directly driven by electricity. Thus, the device can operate in PEC mode during irradiation and switch to an electricity-powered mode in the dark through bypassing of the semiconductor configuration. The bifunctional perovskite-BiVO₄ tandem provides a solar-to-hydrogen efficiency of 1.3% under simulated solar irradiation and an onset for water electrolysis at 1.8 V. The compact design and low cost of the proposed device may provide an advantage over other technologies for round-the-clock fuel production.     

Integrating Assessment and Instruction: Using Student-Generated Grading Criteria to Evaluate Multimodal Digital Projects

In this article, I explore how we can link assessment to instruction and the multimodal composing process by inviting students to generate the grading criteria for new media assignments, and I show how this approach influenced students’ composing and understanding of multimodal texts. I first detail the scaffolding processes I took to help the class learn to construct the evaluative criteria for a digital video project, describing the course curriculum, instructional approaches, and assignments. Then drawing from extended interviews with three learners, I present their perceptions on how the collaborative construction of grading standards affected their learning and comprehension of new media rhetoric. I close with pedagogical recommendations for instructors who teach multimodal digital writing and who seek to integrate the collaborative construction of grading criteria into their classroom.     

Multifunctional,pH‐responsive graft copolymer prepared from deproteinized natural rubber and 4‐vinylpyridine via emulsion polymerization

We investigated the synthesis of a pH‐responsive graft copolymer of natural rubber and 4‐vinylpyridine. The grafting reaction was carried out using deproteinized natural rubber (DPNR) latex, with potassium persulfate as a free radical initiator. The pH responsiveness of the graft copolymer was investigated using water swelling and contact angle measurements, and was compared with that of pure DPNR. The graft copolymer was found to become responsive in solution at a pH of around 4. Indigo carmine adsorption studies identified the Langmuir isotherm, suggesting monolayer coverage. The adsorbed indigo carmine, a model anionic drug, and carbon dots, an emerging nanosized fluorophore, could be released from the graft copolymer by lowering the pH of the solution. The graft copolymer was tested as a heavy metal adsorbent, and demonstrated selectivity to copper(II) ions. The graft copolymer of 4‐vinylpyridine and DPNR developed in this study is therefore a multifunctional, pH‐responsive material with a wide range of potential applications, including sensing and catalysis, as a biomedical material and as an adsorbent. © 2017 Society of Chemical Industry     

Preparation of pH‐responsive crosslinked materials from natural rubber and poly(4‐vinylpyridine)

Stimuli‐responsive elastomers are smart materials for sensing applications. Natural rubber (NR) is a renewable elastomer with excellent elasticity and fatigue resistance. In this work, a straightforward method for the preparation of pH‐responsive crosslinked materials from NR and poly(4‐vinylpyridine) (P4VP) via free radical crosslinking reaction using benzoyl peroxide (BPO) as an initiator is described. The effects of P4VP and BPO concentrations, reaction time and reaction temperature on immobilization percentage were investigated. It was found that the immobilization percentage reached 90% when using a P4VP concentration of 150 phr and a BPO concentration of 10 phr for 24 h at 90 °C. The pH responsiveness of the crosslinked materials was studied via water swelling, water contact angle and dye release measurements. Unlike unmodified rubber, the P4VP‐crosslinked NR was found to be pH‐responsive in acidic solution. Indigo carmine adsorption studies showed the Langmuir isotherm suggesting monolayer coverage of dye on the rubber surface. The dye could also be released upon increasing the pH of solution above 4. Based on these results, the introduction of pH responsiveness to NR will lead to novel responsive rubber‐based materials that can be used in biomedical and sensing applications. © 2016 Society of Chemical Industry     

Multiple degree elevation and constrained multiple degree reduction for DP curves and surfaces

In this paper, the problem of single and multiple degree elevation and reduction for DP curves and surfaces is considered and expressed in matrix representations. Using monomial matrix representations of the univariate DP polynomials, single and multiple degree elevation matrices can be derived by minor extension of this monomial matrix. Given this result, matrices of constrained single and multiple degree reduction can be readily obtained. Finally, important and sufficient conditions for degree reduction can also be found from these resulting matrices.     

Enhanced liquid biofuel production from crude palm oil over synthesized NiMoW-ZSM-5/MCM-41 catalyst

Micro-mesoporous ZSM-5/MCM-41 composites were prepared and then loaded with varied contents of NiMoW by the wet impregnation method. The hydrocracking conversion of crude palm oil to liquid biofuels with the prepared catalysts was carried out in a batch reactor at 400°C for 2 h. ZSM-5/MCM-41 composite exhibited 51.00% conversion with a yield of 9.23% gasoline, 20.60% kerosene, and 21.17% diesel. Upon loading of NiMoW, the catalysts exhibited an improved conversion (≥ 62.60%) and a reduced formation of coke, which resulted from combined properties of ZSM-5 with MCM-41 and the presence of dispersed NiMoW. The contents of impregnated metals also affected the performance of catalysts. Using ANOVA analysis (p < 0.05), we found that 8:8:8 wt.% NiMoW-ZSM-5/MCM-41 catalyst was suitable for the production of biofuels, when considering the efficiency and cost-effectiveness.     

A simple 2D modulation code in single-reader two-track reading BPMR systems

A reduction in the track width of magnetic recording systems results in a welcome increase in Areal Density (AD),but can severely deteriorate system performance...     

ESR studies of a series of phthalocyanines. Mechanism of phototoxicity. Comparative quantitation of O2-. using ESR spin-trapping and cytochrome c reduction techniques

ESR experiments with 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP) and the spin-trap 5,5-dimethyl pyrroline-N-oxide (DMPO) have been performed on a series of new phthalocyanines: the bis(tri-n-hexylsiloxy) silicon phthalocyanine ([(nhex)3SiO]2SiPc), the hexadecachloro zinc phthalocyanine (ZnPcCl16), the hexadecachloro aluminum phthalocyanine (AlPcCl16), the hexadecachloro aluminum phthalocyanine sulfate (HSO4AlPcCl16), whose photocytotoxicity has been studied against various leukemic and melanotic cell lines. Type I and Type II pathways occur simultaneously in DMF although the Type II seems to be prevalent. These results are not changed when the bis(tri-n-hexylsiloxy) silicon phthalocyanine is entrapped into liposomes. By contrast, the Type I process is favored in membrane models for all the perchlorinated phthalocyanines. This modified behavior may be accounted on a possible stacking of phthalocyanines in membranes and a preventing effect of axial ligands against aggregation in the case of the bis(tri-n-hexylsiloxy) silicon phthalocyanine. The photodynamic action of zinc perchlorinated phthalocyanine is not dependent on singlet oxygen, phototoxicity of this molecule being essentially mediated by oxygen free radicals. Quantitation of the superoxide radical was accomplished, with good agreement, by two techniques: the cytochrome c reduction and the ESR quantitation based on the double integration of the first derivative of the ESR signal. The disproportionation of the superoxide radical or degradation of the spin-trap seem to be avoided in aprotic solvents such as DMF.