A series of liquid‐crystalline (LC) π‐‐conjugated oligothiophenes bearing three or two alkoxy chains at their extremities has been designed and synthesized. These polycatenar oligothiophenes form various LC nanostructures including smectic, columnar, and micellar cubic phases. These properties depend on the number and length of the terminal alkoxy chains. The hole mobilities for the oligothiophenes have been measured. The layered smectic and columnar structures are capable of transporting holes, leading to mobilities of up to 0.01 cm2 V−1 s−1. The columnar LC assemblies have also been explored to produce linearly polarized light‐emission. Fine red polarized fluorescence is observed from a uniaxially aligned film of the oligothiophenes. The redox properties of the oligothiophenes both in solutions and in films have been examined. The oligothiophenes exhibit electrochromism upon applying an oxidative potential. The present design strategy is useful for fabricating a variety of functional electro‐active molecular assemblies.
Potential-dependent surface structures of Au (111) and Au(100) single-crystal electrodes in a 50 mM H 2 SO 4 solution were investigated at an atomic level using in situ surface X-ray scattering (SXS) techniques. It was confirmed that both the Au(111) and Au(100) surfaces were reconstructed with an attached submonolayer of an oxygen species, most probably water, at 0 V (vs Ag/AgCl). Results at +0.95 V supported a previously suggested model for both the Au(111) and the Au(100) electrodes that, based on infrared and scanning tunneling microscopy measurements, the surfaces were a (1 × 1) structure with the coadsorbed sulfate anion and hydronium cation (H 3 O + ). At +1.05 V, where a small amount of an anodic current flowed, adsorption of a monolayer of oxygen species was observed on both surfaces. When the single-crystal gold electrodes were electrochemically oxidized at +1.40 V, the expansion of the gold surface by about one monolayer of Au atoms was observed, suggesting the penetration of oxygen into the surface gold layers (i.e., the formation of two layers of surface oxide). When the surface oxide was reduced at +0.65 V, the surface structure returned back to the structure observed at +0.95 V before the oxide formation (i.e., a (1 × 1) structure with coadsorbed sulfate anion and H 3 O + ). When the potential was reduced to 0 V, the surfaces were reconstructed again but with slightly more random structures than those before the potential cycle.
In situ surface X-ray scattering (SXS) measurements were carried out to study the structure of a Ag layer on a Au(111) electrode formed by underpotential deposition (UPD) in sulfuric acid solution. Specular rod profiles showed that a monolayer of Ag was formed at a potential between the second and third UPD peaks, and a bilayer of Ag was formed at a potential between the third UPD peak and bulk deposition. Non-specular rod profiles demonstrated that electrochemically deposited Ag atoms both in the first and second layers were situated at the three-fold hollow cubic closest packing (ccp) site of the underlying Au and Ag layers, respectively.
Background:Immunotherapy with bacillus Calmette-Guérin (BCG) for bladder cancer is successful, although the precise mechanism is unclear. Natural killer (NK) cells are a candidate for BCG-activated killer cells, but the roles of other T lymphocytes, such as NKT cells and gdT cells, are not fully understood. Mycobacterium tuberculosis is a potent activator of both NKT cells and gdT cells. However, it is known that the patient's prognosis is good if there are increased numbers of dendritic cells (DCs) in the urine after BCG therapy. Therefore, we investigated whether DCs are matured by BCG and whether BCG-pulsed DCs stimulate NKT cells and gdT cells. Methods: Naïve Pan T cells were isolated form peripheral blood mononuclear cells (PBMCs) and DCs were obtained by culturing CD14 + monocytes with granulocyte-macrophage colony-stimulating factor and interleukin-4. The DCs were pulsed with BCG and their maturation was measured by fluorescence-activated cell sorter analysis using the CD86 antibody. Naïve T lymphocytes were stimulated by coculture with BCG-pulsed DCs in vitro, followed by FACS analysis to estimate the ratio and activation of NKT cells and the ratio of gdT cells. The 51 Cr (chromium) release assay was used to estimate the cytotoxic activity of the stimulated T cells. Cytolytic proteins in the patient's PBMCs were measured during BCG therapy using semiquantitative reverse transcriptase-polymerase chain reaction. Results: The DCs were matured by BCG stimulation and the number of NKT cells and gdT cells increased after culturing with BCG-pulsed DCs. The BCG-pulsed DCs also activated the NKT cells and gdT cells. Also, the lymphocytes that were cocultured with the BCG-pulsed DCs showed unspecific cytotoxic activity against a bladder cancer cell line. Conclusion: Sensitization of NKT cells and gdT cells by BCG-pulsed DCs might be one of the mechanisms of BCG immunotherapy.
Oxygen sorption/desorption properties of SrCo x Fe1–x O3−δ were examined as an oxygen sorbent for a high-temperature pressure-swing adsorption (HT-PSA) process. Perovskite-type structure of the SrCo x Fe1–x O3−δ powder samples was observed in the composition range of 0 ≤ x ≤ 0.85, by using XRD measurements. A temperature-programmed-desorption (TPD) measurement revealed that the oxygen desorption temperature in N2 for the perovskite-type SrCo x Fe1–x O3−δ samples was lowered with increasing x. Consequently, the oxygen desorption temperature of the SrCo0.85Fe0.15O3−δ sample exhibited around 300 °C, which was the lowest of those of the examined samples. A high-temperature X-ray diffraction (HT-XRD) measurement suggested that the oxygen desorption of SrCo0.85Fe0.15O3−δ in N2 occurred, accompanying the phase transition from perovskite-type structure to brownmillerite structure. Isothermal oxygen sorption/desorption behavior of the SrCo x Fe1–x O3−δ samples was examined by means of thermogravimetric analysis (TGA). As a result, it was confirmed that the amount of sorbed oxygen for the SrCo0.85Fe0.15O3−δ sample gave 11.7 cm3 g–1 at 300 °C, which was larger than that (8.6 cm3 g–1) for a benchmark oxygen sorbent (La0.1Sr0.9Co0.9Fe0.1O3−δ). In order to obtain oxygen-enriched air by using the SrCo0.85Fe0.15O3−δ pellet sample as the oxygen sorbent, the oxygen separation from synthetic air was carried out by using a small-scale PSA apparatus equipped with a vacuum pump. It was confirmed that the 45 vol % oxygen-enriched air was obtained even at 300 °C, by using this apparatus.
The in vivo responsiveness of thyroid glands to TSH at various ages in novel 'growth-retarded' (grt/grt) mice derived from Snell's dwarf (DW/J) mice and in their normal counterparts were analysed by determining serum T4 concentrations before and after the administration of exogenous TSH. The serum T4 concentration in normal mice increased in response to TSH at 2, 4 and 12 weeks of age but not at 1 week of age. A transient augmentation of such thyroidal responsiveness to TSH was apparent in normal mice at 2 weeks of age, when the serum T4 level exhibits a peak and the pubertal growth of mice starts. In contrast to normal mice, at any age examined from 2 to 12 weeks after birth, exogenous TSH did not influence serum T4 concentrations in the grt/grt mice at all. On the other hand, serum TSH concentrations in young grt/grt mice were highly elevated compared with those in normal mice and they were normalized by a 2-3 week's treatment with T3. Morphological studies demonstrated degenerated thyroid glands in the grt/grt mice. These results suggest that the severe hypothyroidism and consequent growth retardation in growth-retarded mice are due to impairment of the thyroid glands of the mutant mice in producing and/or secreting thyroid hormones in response to TSH.
Ag/AgCl reaction at the Ag bilayer, which was underpotentially prepared on a Au(111) surface, was investigated using electrochemical quartz crystal microbalance (EQCM), scanning tunneling microscopy (STM), surface X-ray scattering (SXS), and electrochemical techniques. When the potential was scanned positively from -200 mV, the Cl^[-] ion was adsorbed on the Au(111) electrode surface around 0 mV, and then the phase transition of the adsorbed Cl^[-] ion layer from random orientation to (√3 x √3) structure took place at around +130 mV. The Ag bilayer and Cl^[-] ions were oxidatively reacted to form the AgCl monolayer with (√13 x √13)R13.9° structure around +200 mV, accompanied with the formation of AgCl monocrystalline clusters on the AgCl monolayer surface. The structure of the AgCl monolayer on the Au(111) surface was changed from (√13 x √13)R13.9° structure to (4 x 4) structure around +500 mV. When the potential was scanned back negatively, the AgCl monolayer was electrochemically reduced, and a Ag monolayer, not a bilayer, was formed on the Au(111) surface. In the subsequent potential cycles, the structural change between the Ag monolayer and the AgCl monolayer was reversibly observed. All oxidative structural changes were much slower than the reductive ones
Achieving multiple physical properties from a single material through three-dimensional (3D) printing is important for manufacturing applications. In addition, industrial-level durability and reliability is necessary for realizing individualized manufacturing of devices using 3D printers. We investigated the properties of architected materials composed of ultraviolet (UV)-cured urethane elastomers for use as insoles. The durability and reliability of microlattice and metafoam architected materials were compared with those composed of various foamed materials currently used in medical insoles. The hardness of the architected materials was able to be continuously adjusted by controlling the design parameters, and the combination of the two materials was effective in controlling rebound resilience. In particular, the features of the architected materials were helpful for customizing the insole properties, such as hardness, propulsive force, and shock absorption, according to the user’s needs. Further, using elastomer as a component led to better results in fatigue testing and UV resistance compared with the plastic foam currently used for medical purposes. Specifically, polyethylene and ethylene vinyl acetate were deformed in the fatigue test, and polyurethane was mechanically deteriorated by UV rays. Therefore, these architected materials are expected to be reliable for long-term use in insoles.
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