Zinc Phthalocyanine–Graphene Hybrid Material for Energy Conversion: Synthesis, Characterization, Photophysics, and Photoelectrochemical Cell Preparation

Graphene exfoliation upon tip sonication in <i>o</i>-dichlorobenzene (<i>o</i>-DCB) was accomplished. Covalent grafting of (2-aminoethoxy)­(tri-<i>tert</i>-butyl) zinc phthalocyanine (ZnPc) to exfoliated graphene sheets was then achieved. The newly formed ZnPc–graphene hybrid material was found to be soluble in common organic solvents without any precipitation for several weeks. Application of diverse spectroscopic techniques verified the successful formation of the ZnPc–graphene hybrid material, while thermogravimetric analysis revealed the amount of ZnPc loading onto graphene. Microscopy analysis based on AFM and TEM was applied to probe the morphological characteristics and to investigate the exfoliation of graphene sheets. Efficient fluorescence quenching of ZnPc in the ZnPc–graphene hybrid material suggested that photoinduced events occur from the photoexcited ZnPc to exfoliated graphene. The dynamics of the photoinduced electron transfer was evaluated by femtosecond transient absorption spectroscopy, thus revealing the formation of transient species such as ZnPc^•+, yielding the charge-separated state ZnPc^•+–graphene^•–. Finally, the ZnPc–graphene hybrid material was integrated into a photoactive electrode of an optical transparent electrode (OTE) cast with nanostructured SnO₂ films (OTE/SnO₂), which exhibited stable and reproducible photocurrent responses, and the incident photon-to-current conversion efficiency was determined

<i>P. gingivalis</i> up-regulates FOXO1 and FOXO3 mRNA levels.

<p>Primary human gingival epithelial cell cultures were incubated with or without <i>P. gingivalis</i> at MOI = 1∶50 for 20 hrs. In some cases cells were pre-incubated with FOXO1 siRNA (SiFOXO1), FOXO3 siRNA (SiFOXO3) or scrambled siRNA (SiScr) FOXO1 prior to stimulation with bacteria. FOXO1 and FOXO3 mRNA levels were measured by real-time PCR. * Significantly different from control cells without bacterial stimulation (P<0.05). ** Significantly different between scrambled siRNA and FOXO1 or FOXO3 siRNA (P<0.05). + Significantly different between FOXO1 siRNA and FOXO3 siRNA (P<0.05).</p

<i>P. gingivalis</i> but not <i>F. nucleatum</i> or <i>S. gordonii</i> induces expression of differentiation markers.

<p>Primary human gingival epithelial cell cultures were incubated with or without exposure to an air-liquid-interface to induce differentiation and then challenged with <i>P. gingivalis</i> (Pg), S. <i>gordonii</i> (Sg), or <i>F. nucleatum</i> (Fn) at 2×10⁸/cm² for 24 hrs. mRNA levels of keratin-1 or keratin-10 were measured by real-time PCR. +Significant difference between undifferentiated and differentiated cells (P<0.05). * Significantly different from matched control (P<0.05).</p

<i>P. gingivalis</i> induces gingival epithelial cell apoptosis through FOXO1 or FOXO3.

<p>Primary human gingival epithelial cells were incubated with or without P. gingivalis at MOI = 1∶10 or 1∶50 for overnight. In some cases cells were pre-incubated with FOXO1 siRNA (SiFOXO1), FOXO3 siRNA (SiFOXO3) or scrambled siRNA (SiScr) prior to incubation with bacteria. Apoptotic cells were assessed by the TUNEL assay. * Significantly different from control cells with bacterial stimulation (P<0.05). ** Significantly different between scrambled siRNA and FOXO1 or FOXO3 siRNA (P<0.05).</p

FOXO1 and FOXO3 regulate basal and <i>P. gingivalis</i> up-regulated mRNA levels of TLR2 and TLR4.

<p>Primary human gingival epithelial cell cultures were incubated with or without <i>P. gingivalis</i> at MOI = 1∶50 for 20 hrs. In some cases cells were pre-incubated with FOXO1 siRNA (SiFOXO1), FOXO3 siRNA (SiFOXO3) or scrambled siRNA (SiScr) FOXO1 prior to stimulation with bacteria. Real-time PCR was used to measure mRNA levels of TLR-2 and TLR-4. * Significantly different from control cells without bacterial stimulation (P<0.05). ** Significantly different between scrambled siRNA and FOXO1 or FOXO3 siRNA (P<0.05). + Significantly different between FOXO1 siRNA and FOXO3 siRNA (P<0.05).</p

<i>P. gingivalis</i> up-regulation of keratinocyte differentiation markers is FOXO1 or FOXO3 dependent.

<p>Primary human gingival epithelial cell cultures were incubated with or without <i>P. gingivalis</i> at MOI = 1∶50 for 20 hrs. In some cases cells were pre-incubated with FOXO1 siRNA (SiFOXO1), FOXO3 siRNA (SiFOXO3) or scrambled siRNA (SiScr) FOXO1 prior to stimulation with bacteria. Real-time PCR was used to measure mRNA levels of keratin-1, keratin-10, involucrin and keratin-14. * Significantly different from control cells without bacterial stimulation (P<0.05). ** Significantly different between scrambled siRNA and FOXO1 or FOXO3 siRNA (P<0.05). + Significantly different between FOXO1 siRNA and FOXO3 siRNA (P<0.05).</p

Synthesis and Photophysical Properties of Conjugated and Nonconjugated Phthalocyanine–Perylenediimide Systems

The synthesis and characterization of different conjugated phthalocyanine–perylenemonoimidebenzimidazole [ZnPc-PBIm­(OR)₄] and nonconjugated phthalocyanine–perylenediimide [ZnPc-PDI­(OR)₄] dyads are carried out. UV–vis, ¹H NMR, and electrochemistry measurements reveal the interaction between perylene and phthalocyanine moieties in the ground state in the conjugated hybrid and the lack of interaction in the nonconjugated one. Ultrafast transient absorption measurements show that a state with substantial charge-transfer character is formed in both compounds, but the rates for the formation and recombination from this state are much faster for the conjugated compound

Expressed sequence tag (EST) data for the <i>S. stercoralis</i> L3i.

<p>Expressed sequence tag (EST) data for the <i>S. stercoralis</i> L3i.</p

KEGG pathways of putative proteins inferred from the transcriptome of <i>S. stercoralis</i> L3i.

<p>KEGG pathways of putative proteins inferred from the transcriptome of <i>S. stercoralis</i> L3i.</p

Sequence homology inferred between <i>S. stercoralis</i> current dataset and other datasets.

<p>Sequence homology inferred between <i>S. stercoralis</i> current dataset and other datasets.</p