The enigmatic self-assembling ability of nanodiamond (ND) particles has been discovered herein. Diamond-rich crystalline nanosheets with thickness of approximately â¼25 nm were grown from a Langmuir monolayer of arachidic acid (AA) at the interface between air and a dilute aqueous ND solution. Their fine rectangular shapes with uniform uniaxial birefringence indicate appreciable crystallinity, thus supporting that they are hydrated colloidal crystals of homogeneous ND particles.
An ambient-stable radical cation of a Thiele's hydrocarbon derivative has been synthesized and its properties have been explored using a combined experimental and computational approach. The radical cation exhibited several intense near-infrared absorption bands and its solution-processed thin films showed high electrical conductivity at room temperature.
Spherulitic crystallization in Langmuir-Blodgett (LB) films of the ditetradecyldimethylammonium-Au(dmit)2 [2C14N+Me2-Au(dmit)2] salt has been characterized by polarized light microscopy, Fourier-transform infrared (FT-IR) spectroscopy, and X-ray diffraction (XRD) analyses. Analyses by differential scanning calorimetry (DSC) for the bulk crystals indicate that annealing in the temperature range of 58-100 °C may be appropriate to improve the order in the LB film. The polarized light microscopy measurement further revealed that a spherulite structure was formed after the film was annealed at 80 °C for 60 min. FT-IR spectroscopy measurements demonstrated that the order of the principal hydrocarbon chains was improved and that the rotation of CH3 groups was hindered by the annealing. Out-of-plane XRD analyses revealed that the d-spacing of the 2C14N+Me2-Au(dmit)2 LB film changed from 3.1 to 2.5 nm upon annealing. We hypothesize that a layered structure with interdigitated hydrocarbon chains, which is equivalent to or close to that of the corresponding bulk crystal, has been realized in the LB film by annealing. We consider that two different kinds of one-dimensional (1D) interactions along the a-axis are the driving forces to realize the spherulite structure in the LB system; one is an extended 1D contact due to the pronounced interdigitation of the alkyl chains of the ammonium ion, which plays a role similar to that of the folding of chains in the lamellar structures of polymers, and the other is a 1D extended sulfur-sulfur contact between Au(dmit)2 dimer pairs. So far, spherulite formation in LB films has been reported almost exclusively for polymerized materials. Here, we demonstrate that a spherulite texture can also be formed in LB films based on nonpolymerized materials via the interdigitation of hydrocarbon chains, leading to a new well-ordered state.
We report synthesis and characterization of near-infrared (NIR)-absorbing/emitting Thiele's hydrocarbon derivatives, in which four aryl groups are bridged to a quinodimethane skeleton. The quinoid structure of the bridged-tetra-aryl- p-quinodimethanes (BTAQs) was confirmed by spectroscopic, X-ray crystallographic, and computational methods. Although quinodimethane derivatives with a small HOMO-LUMO energy gap often exhibit biradical character, BTAQs showed no biradical character. Instead, they exhibited two-step near-infrared electrochromism. The donor/acceptor properties of the aryl groups were found to play a key role in the unique properties of BTAQs.
The temperature and concentration dependencies of the crystallization of two small-molecular semiconductors were clarified by constructing quasi-phase diagrams at air/oil interfaces and in bulk oil phases. A quinoidal quaterthiophene derivative with four alkyl chains (QQT(CN)4) in 1,1,2,2-tetrachroloethane (TCE) and a thienoacene derivative with two alkyl chains (C8-BTBT) in o-dichlorobenzene were used. The apparent crystal nucleation temperature (Tn) and dissolution temperature (Td) of the molecules were determined based on optical microscopy examination in closed glass capillaries and open dishes during slow cooling and heating processes, respectively. Tn and Td were considered estimates of the critical temperatures for nuclear formation and crystal growth, respectively. The Tn values of QQT(CN)4 and C8-BTBT at the air/oil interfaces were higher than those in the bulk oil phases, whereas the Td values at the air/oil interfaces were almost the same as those in the bulk oil phases. These Gibbs adsorption phenomena were attributed to the solvophobic effect of the alkyl chain moieties. The temperature range between Tn and Td corresponds to suitable supercooling conditions for ideal crystal growth based on the suppression of nucleation. The Tn values at the water/oil and oil/glass interfaces did not shift compared with those of the bulk phases, indicating that adsorption did not occur at the hydrophilic interfaces. Promotion and inhibition of nuclear formation for crystal growth of the semiconductors were achieved at the air/oil and hydrophilic interfaces, respectively.
We report on the use of microcrystallization in capillaries to fabricate patterned crystalline microstructures of the low-bandgap ambipolar quinoidal quaterthiophene derivative (QQT(CN)4) from a chloroform solution. Aligned needle-shaped QQT(CN)4 crystals were formed in thin film microstructures using either open- or closed- capillaries made of polydimethylsiloxane (PDMS). Their charge transport properties were evaluated in a bottom-gate top-contact transistor configuration. Hole and electron mobilities were found to be as high as 0.17 and 0.083 cm(2) V(-1) s(-1), respectively, approaching the values previously obtained in individual QQT(CN)4 single crystal microneedles. It was possible to control the size of the needle crystals and the microline arrays by adjusting the structure of the PDMS mold and the concentration of QQT(CN)4 solution. These results demonstrate that the microcrystallization in capillaries technique can be used to simultaneously pattern organic needle single crystals and control the microcrystallization processes. Such a simple and versatile method should be promising for the future development of high-performance organic electronic devices.
Highly oriented J-aggregates of a nitroazo dye were obtained in solid thin films on aligned poly(tetrafluoroethylene) surfaces. During film deposition on a friction-transferred poly(tetrafluoroethylene) layer, a sharp peak grew in the polarized absorption spectra around 613 nm, which was red-shifted 117 nm from the peak in dilute dichloromethane solution. The peak showed remarkable optical anisotropy: dichroic ratios D of up to 22 were observed, and the intrinsic D value should substantially exceed this value. These results indicate that the peak is attributable to highly oriented J-aggregates. On glass, however, H-like aggregates grew, exhibiting an absorption peak at 410 nm. Hence, the substrate surface induced the remarkable chromism observed as a 203 nm red shift.
High-performance non-volatile memory that can operate under various mechanical deformations such as bending and folding is in great demand for the future smart wearable and foldable electronics. Here we demonstrate non-volatile solution-processed ferroelectric organic field-effect transistor memories operating in p- and n-type dual mode, with excellent mechanical flexibility. Our devices contain a ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) thin insulator layer and use a quinoidal oligothiophene derivative (QQT(CN)4) as organic semiconductor. Our dual-mode field-effect devices are highly reliable with data retention and endurance of >6,000 s and 100 cycles, respectively, even after 1,000 bending cycles at both extreme bending radii as low as 500 µm and with sharp folding involving inelastic deformation of the device. Nano-indentation and nano scratch studies are performed to characterize the mechanical properties of organic layers and understand the crucial role played by QQT(CN)4 on the mechanical flexibility of our devices.
Here, we discuss the local photovoltaic characteristics of a structured bulk heterojunction, organic photovoltaic devices fabricated with a liquid carbazole, and a fullerene derivative based on analysis by scanning kelvin probe force microscopy (KPFM). Periodic photopolymerization induced by an interference pattern from two laser beams formed surface relief gratings (SRG) in the structured films. The surface potential distribution in the SRGs indicates the formation of donor and acceptor spatial distribution. Under illumination, the surface potential reversibly changed because of the generation of fullerene anions and hole transport from the films to substrates, which indicates that we successfully imaged the local photovoltaic characteristics of the structured photovoltaic devices. Using atomic force microscopy, we confirmed the formation of the SRG because of the material migration to the photopolymerized region of the films, which was induced by light exposure through photomasks. The structuring technique allows for the direct fabrication and the control of donor and acceptor spatial distribution in organic photonic and electronic devices with minimized material consumption. This in situ KPFM technique is indispensable to the fabrication of nanoscale electron donor and electron acceptor spatial distribution in the devices.
Donor and acceptor spatial distributions were directly formed in a surface relief grating of structured bulk heterojunction (BHJ) photovoltaic devices by simple periodic photopolymerization. Enhanced photocurrents were observed in the structured BHJ photovoltaic devices and formation of the D/A spatial distribution was confirmed by Kelvin probe force microscopy. This technique enables the fabrication of structured BHJ photovoltaic devices with solution-processable organic semiconductors, and has tremendous potential for controlling D/A spatial distribution in organic optoelectronics devices.
Carbazoles/chemistry , Electrons , Fullerenes/chemistry , Photochemical Processes/radiation effects , Polymerization/radiation effects , Electrochemistry/instrumentation , Electrodes , Molecular Structure , Semiconductors/instrumentation , Surface Properties , Tin Compounds/chemistry
Emulsions comprising a dual-surfactant system of a long-chain amidoamine derivative and a quaternary ammonium salt developed an iridescent color at a specific temperature region. The emulsions underwent phase inversion on heating from an O/W emulsion to a W/O emulsion, passing through a periodical lamellar structure which developed a characteristic interference color. Interestingly, the color and the coloring temperature can be independently controlled by adjusting the concentration of surfactants, respectively.
We have previously shown that transduction of HOXD3, one of homeobox genes, into human lung cancer A549 cells enhances cell motility, invasion and metastasis. In the present study, we examined the roles of integrin beta3 which was up-regulated by HOXD3-overexpression in the HOXD3-induced motility of A549 cells. We first established integrin beta3-transfectants and compared their motile activity to those of the HOXD3-transfected, control-transfected and parental cells by three different assays. The integrin beta3-transfectants as well as the HOXD3-transfectants formed heterodimer with integrin alphav subunit, and showed highly motile activities assessed by haptotaxis or phagokinetic track assay compared to the control transfectants or parental cells. In vitro wound-healing assay revealed that migratory activities were graded as the HOXD3-transfectants > the integrin beta3-transfectants > the control transfectants or parental cells. E-cadherin was expressed in the integrin beta3-transfectants but not expressed in the HOXD3-transfectants. An addition of function-blocking antibody to E-cadherin into the wound-healing assay promoted the migratory activity of the integrin beta3-transfectants, suggesting that E-cadherin prevented the cells from dissociating from the wound edges. These results indicate that increased expression of integrin alphav beta3 and loss of E-cadherin by HOXD3-overexpression are responsible for the enhanced motility and dissociation.
Cadherins/physiology , DNA-Binding Proteins/physiology , Homeodomain Proteins/physiology , Integrin alphaVbeta3/physiology , Lung Neoplasms/pathology , Animals , Cell Line, Tumor , Cell Movement , Humans , Mice , Neoplasm Metastasis , Signal Transduction , Transcription Factors , Transforming Growth Factor beta/pharmacology , Wound Healing
The semiconducting film based on bis(o-diiminobenzosemiquinonate) nickel(II) complex showed uniaxial orientation structure along the normal to the substrate and good p-type metal-organic thin-film transistor (MOTFT) character.
Steady-state and time-resolved photoluminescence (PL) measurements on vapor deposited films of a non-ionic bisazomethine dye have been performed. In the films, it is possible to control the ratio between J-aggregate and crystalline phases of the dye by means of exposure to chloroform vapour, and thus the origin of PL can be determined from comparison between several films. In the films, PL was emitted exclusively from the crystalline phase. Although the origin of PL was not from the J-aggregate phase, some features of the observed PL were very similar to those reported for J-aggregates of ionic dyes. We also found that these features in the vapor deposited films were caused by a competition between free excitons and excitons trapped at defect sites.
Azo Compounds/chemistry , Coloring Agents/chemistry , Thiosemicarbazones/chemistry , Crystallization , Luminescent Measurements , Temperature , Thermodynamics , Time Factors
The degree of E- and P-cadherin expressions inversely correlate with the progression stage of human melanoma. In the present study, we analyzed mechanisms of down-regulation of E- and P-cadherin gene expressions in 8 human melanoma cell lines. In 5 of the 8 melanoma cell lines, E-cadherin expression was lost or markedly decreased compared to that in normal melanocytes, and 4 of the 5 melanoma cell lines lost P-cadherin expression. All of the melanoma cell lines expressed snail, which is known to encode a transcription repressor for E-cadherin, at a higher level than melanocytes whereas expression levels of the snail varied among cell lines. Transduction of snail gene into MMAc cells which expressed a high level of E-cadherin and an extremely low level of snail decreased expression of E-cadherin but not P-cadherin. In contrast, transduction of antisense-snail gene into A375M cells which expressed no E-cadherin and a high level of snail restored expression of E-cadherin but not P-cadherin. Methylation-specific PCR analysis revealed CpG methylation in the promoter region of E-cadherin of MeWo and AKI cells. Further, the treatment with a demethylating agent, 5-azacytidine led AKI and A375M cells to re-express both E- and P-cadherin. The results show E-cadherin gene is silenced by at least two distinct mechanisms (methylation and transrepression by Snail) in human melanoma cell lines whereas P-cadherin gene seems to be silenced by methylation but not by snail.
Cadherins/biosynthesis , Gene Expression Profiling , Gene Silencing , Melanoma/genetics , Melanoma/pathology , Skin Neoplasms/genetics , Skin Neoplasms/pathology , DNA Methylation , DNA-Binding Proteins/pharmacology , Down-Regulation , Humans , Promoter Regions, Genetic , Snail Family Transcription Factors , Transcription Factors/pharmacology , Tumor Cells, Cultured , Zinc Fingers
In human genetics and molecular oncology, mutation research is necessary not only to identify mutations in nucleic acid sequences, but also to analyze the loss of function caused by mutant proteins. We reconstructed a protein-protein network system of human beta-catenin and TCF4, in Saccharomyces cerevisiae. beta-Catenin and TCF4 proteins form a complex and transactivate reporter genes. Co-expressed wild-type APC with beta-catenin and TCF4 inhibit the transcriptional activity of the beta-catenin/TCF4 complex in yeast, as well as in mammals. This unique method in which the beta-catenin/TCF4 signaling pathway is reconstructed in vivo may prove useful for the functional evaluation of APC mutants, including a type of APC truncated and missense mutants influenced to the ability of binding to beta-catenin.
Cytoskeletal Proteins/physiology , DNA-Binding Proteins/physiology , Genes, APC , Mutation/physiology , Saccharomyces cerevisiae/metabolism , Signal Transduction , Trans-Activators/physiology , Transcription Factors/physiology , Colorectal Neoplasms/diagnosis , Cytoskeletal Proteins/genetics , DNA-Binding Proteins/genetics , Gene Expression , Humans , Mutation, Missense/physiology , TCF Transcription Factors , Trans-Activators/genetics , Transcription Factor 7-Like 2 Protein , Transcription Factors/genetics , Transcription, Genetic/physiology , beta Catenin
This is the first report of J-aggregate formation of a non-ionic bisazomethine dye in vapor deposited films; this dye allows us to prepare easily large homogeneous and very stable J-aggregate thin films and to investigate intrinsic properties of low-dimensional Frenkel excitons.
BACKGROUND: Epidemiological studies have shown a correlation between Helicobacter pylori infection and human gastric carcinogenesis. A Mongolian gerbil model has demonstrated that H. pylori infection induced gastric carcinoma. However, the disadvantage of this animal model is a lack of information regarding the cellular genes involved in oncogenesis. Mutation of the p53 gene is one of the most common steps in gastric carcinogenesis. In this study, we aimed to clone the p53 gene of the Mongolian gerbil and detect the functional mutations in H. pylori-infected animals. MATERIALS AND METHODS: The p53 complementary DNA (cDNA) of Mongolian gerbil was cloned by the methods of reverse-transcribed polymerase chain reaction and rapid amplification of cDNA ends. RESULTS: The p53 cDNA of Mongolian gerbil has a 78.8% homology to that of humans. A novel yeast p53 assay system was established and enabled to detect the functional mutations of the p53 gene in the stomach of the Mongolian gerbil. CONCLUSIONS: This is the first report of the complete sequence of wild-type p53 cDNA of the Mongolian gerbil. This genetic information and an assay system designed to detect the functional mutations of the p53 gene are useful for further investigations of gastric oncogenesis in this animal model.
Tumor Suppressor Protein p53/genetics , Yeasts/genetics , Animals , Base Sequence , Cloning, Molecular , DNA, Complementary , Disease Models, Animal , Genetic Vectors , Gerbillinae , Helicobacter Infections/complications , Helicobacter pylori , Molecular Sequence Data , Plasmids , Stomach Neoplasms/genetics , Stomach Neoplasms/microbiology
