We have prepared a push-pull porphyrin with an electron-donating triarylamino group at the β,β'-edge through a fused imidazole group and an electron-withdrawing carboxyquinoxalino anchoring group at the opposite β,β'-edge (ZnPQI) and evaluated the effects of the push-pull structure of ZnPQI on optical, electrochemical, and photovoltaic properties. ZnPQI showed red-shifted Soret and Q bands relative to a reference porphyrin with only an electron-withdrawing group (ZnPQ), thus demonstrating the improved light-harvesting property of ZnPQI. The optical HOMO-LUMO gap was consistent with that estimated by DFT calculations. The ZnPQI-sensitized solar cell exhibited a relatively high power conversion efficiency (η) of 6.8 %, which is larger than that of the ZnPQ-sensitized solar cell (η=6.3 %) under optimized conditions. The short-circuit current and fill factor of the ZnPQI-sensitized solar cell are larger than those of the ZnPQ-sensitized solar cell, whereas the open circuit potential of the ZnPQI-sensitized cell is smaller than that of the ZnPQ-sensitized cell, leading to an overall improved cell performance of ZnPQI. Such fundamental information provides a new tool for the rational molecular design of highly efficient dye-sensitized solar cells based on push-pull porphyrins.
Dense arrays of zinc oxide nanorods with high specific
surface
areas were grown by hydrothermal method and functionalized by self-assembled
monolayer (SAM) of porphyrins. The growth process was optimized to
obtain dense arrays of nanorods with diameter of 60–80 nm and
length up to 1.5 μm. The increase in the effective surface area
was monitored by comparing the absorbances of SAM deposited both on
the flat and nanorod surfaces of ZnO. To alter further semiconductor-organic
SAM interactions, a 2 or 5 nm thick layer of either Al2O3 or TiO2 was deposited on the ZnO nanorods.
The present results show that both carboxylic acid and triethoxysilane
anchors can be used to form porphyrin SAMs on the studied metal oxide
substrates, and the electronic interactions between the metal oxide
and porphyrin SAM are strongly modified by a thin layer of Al2O3 or TiO2. These hybrid semiconductor-organic
SAM constructions present promising model systems for advanced spectroscopy
studies of semiconductor-organic interfaces with high degree of control
over electronic interactions and system morphology.
The adhesion and contact guidance of human primary osteogenic sarcoma cells (Saos-2) were characterized on smooth, microstructured (MST) and micro- and nano-structured (MNST) polypropylene (PP) and on the same samples with a silicon-doped carbon nitride (C(3)N(4)-Si) coating. Injection molding was used to pattern the PP surfaces and the coating was obtained by using ultra-short pulsed laser deposition (USPLD). Surfaces were characterized using atomic force microscopy and surface energy components were calculated according to the Owens-Wendt model. The results showed C(3)N(4)-Si coated surfaces to be significantly more hydrophilic than uncoated ones. In addition, there were 86% more cells in the smooth C(3)N(4)-Si coated PP compared to smooth uncoated PP and 551%/476% more cells with MST/MNST C(3)N(4)-Si coated PP than could be obtained with MST/MNST uncoated PP. Thus the adhesion, spreading and contact guidance of osteoblast-like cells was effectively improved by combining surface texturing and deposition of osteocompatible C(3)N(4)-Si coating.
Condensation of 1,8-naphthalic anhydride with N,N-(dimethylamino)aniline produced the donor-acceptor compound DMIM, which crystallised from a chloroform–diethyl ether mixture to afford two different coloured crystal polymorphs.
A novel donor–acceptor-conjugated polymer PBITT
consisting
of isothianaphthene (ITN) dimer donor unit and thiazolothiazole acceptor
unit was synthesized by thermal conversion method. First, a soluble
precursor polymer with an alternating main chain structure of bicyclo[2.2.2]octadiene
(BCOD)-fused thiophene dimer and benzodithiophene (PPBITT) was synthesized
by palladium(0)-catalyzed Stille coupling reaction. The BCOD moiety
underwent the retro-Diels–Alder reaction by the thermal treatment
of a red PPBITT film to afford a dark blue film of PBITT that was
insoluble in any organic solvents. The optical bandgap of PBITT (1.3
eV) became significantly narrow compared with that of PPBITT (2.1
eV) due to the stabilized quinoid resonance structure of the PBITT
main chain. The field-effect hole mobility (μh) of
PBITT was determined to be 2.2 × 10–4 cm2 V–1 s–1 with on–off
ratio (I
on/I
off) of 2.5 × 102, whereas the corresponding PPBITT-based
device did not show any p- and n-type response. Organic photovoltaic
(OPV) devices were fabricated based on the bulk heterojunction film
of the polymers and [6,6]-phenyl-C61-butyric acid methyl
ester (PCBM). The device with the PBITT:PCBM film exhibited higher
short-circuit current and lower open-circuit voltage than those of
the PPBITT:PCBM-based device, resulting in the comparable power conversion
efficiency (∼0.3%). These results obtained here will provide
fundamental information on the design of thermally induced donor–acceptor
alternating polymers for organic electronics.
Lubricant-treated ultra high molecular weight polyethylene (UHMWPE) composites were prepared by compression molding. Composites were made from mixtures containing up to 5.0 wt % of lubricant. Two solid lubricants, molybdenum disulfide (MoS 2 ), and carbon black (CB), and one liquid lubricant, perfluoropolyether (PFPE), were used in the study. UHMWPE and the lubricants formed 3D networks, where the lubricant was evenly spread over the UHMWPE particles. The amounts of MoS 2 and CB were determined by thermogravimetric analyses, and the amounts of PFPE by ATR-IR spectroscopy. All the lubricant treated composites showed better friction properties than pure UHMWPE. The addition of PFPE to UHMWPE improved the hydrophobicity of the surface, whereas the addition of solid lubricant had little effect.
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