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Organic material-based thermal switch is drawing much attention as one of the key thermal management devices in organic electronic devices. This study aims at tuning the switching temperature (

The fast living polymerization of chiral arylisocyanide in the presence of the aromatic nucleophile adduct of tetra(t-butylisocyano)nickel(II) complex as an initiator gave the predominantly one-handed helical polyisocyanide with narrow polydispersity. X-ray crystal structures of initiators and MALDI-TOF MS and NMR studies of the polymer products elucidated the key role of the aromatic substituents in the initiator and monomer achieving narrow polydispersity. The aromatic groups in the initiator and monomer stabilized the electronic structure of the carbene-like ligand to suppress dissociation of the active nickel complex that leads to chain transfer and termination. The aromatic groups also controlled the reactivity of the active site for initiation and propagation.

In-plane mesopatterns derived from block-copolymer (BCP) micro-phase segregation in thin films have attracted much interest in practical applications as well as fundamental research programs. However, phase segregation along the film-normal direction has been less studied. Here, we describe a strategy to concurrently, yet independently, control in-plane micro-phase and out-of-plane macro-phase segregation in multiblended films composed of liquid-crystalline BCPs (LCBCPs), affording spontaneously layered three-dimensional (3D) mesostructures. This strategy relies on sequential liquid crystallization during the cooling process in thermal annealing as follows. The constituent LCBCP with the highest isotropic-transition temperature (T(iso)) first liquid-crystallizes and segregates from the other LCBCP mixture remaining in isotropic states to form a noncontaminated layer at the top surface. This preformed LCBCP layer preserves its inherent in-plane pattern and acts as a template guiding the subsequent micro-phase segregations of the other low-T(iso) LCBCPs underneath. This self-template–assisted micro-phase segregation (STAMPS) readily provides 3D mesostructures, the potential toward rational material design of which is also demonstrated in water-separation applications.

An ice/salt-assisted strategy has been developed to achieve the green and efficient synthesis of ultrathin two-dimensional (2D) micro/mesoporous carbon nanosheets (CNS) with the dominant active moieties of Fe-N4 (Fe-N-CNS) as high-performance electrocatalysts for the oxygen reduction reaction (ORR). The strategy involves freeze-drying a mixture of iron porphyrin and KCl salt using ice as template followed by a confined pyrolysis with KCl as an independent sealed nanoreactor to facilitate the formation of 2D carbon nanosheets, N incorporation, and porosity creation. The well-defined assembly of ultrathin 2D carbon nanosheets ensures high utilization of D1 and D3 Fe-N4 active sites, and effectively promotes the mass transport of ORR reactants by virtue of the pronounced mesoporous structure. The resulting Fe-N-CNS electrocatalyst was shown to exhibit superior ORR activity, better electrochemical durability, and methanol tolerance towards ORR in alkaline electrolyte relative to the commercial Pt/C electrocatalyst.

Herein, we report the synthesis of a new type of poly(aryleneethynylene) (PAE) comprising electron-deficient tetrafluoroarene units in the π-conjugated backbone and water-solubilizing oligoether (OE) side chains. The fluorinated PAEs were synthesized using a transition-metal-free polymerization system promoted by fluoride anions. Long OE side chains typically retard the polymerization. However, this is resolved by using a tBuOK initiator with a large excess of cryptand-222. The present fluorinated PAEs display spectrophotometrically sufficient solubility in water, high fluorescence quantum yields, and reductive fluorescence quenching by arylamines.

The capability for actual measurements—not just simulations—of the dynamical behavior of THz electromagnetic waves, including interactions with prevalent 3D objects, has become increasingly important not only for developments of various THz devices, but also for reliable evaluation of electromagnetic compatibility. We have obtained real-time visualizations of the spatial evolution of THz electromagnetic waves interacting with a single metal micro-helix. After the micro-helix is stimulated by a broadband pico-second pulse of THz electromagnetic waves, two types of anisotropic re-emissions can occur following overall inductive current oscillations in the micro-helix. They propagate in orthogonally crossed directions with different THz frequency spectra. This unique radiative feature can be very useful for the development of a smart antenna with broadband multiplexing/demultiplexing ability and directional adaptivity. In this way, we have demonstrated that our advanced measurement techniques can lead to the development of novel functional THz devices., 微小金属らせんとテラヘルツ光との相互作用を可視化 --次世代超高速移動通信などにおける高性能アンテナへ応用--. 京都大学プレスリリース. 2021-02-09.

Patient: Male, 62 Final Diagnosis: Enteritis Symptoms: Diarrhea • enteritis Medication: Nivolumab Clinical Procedure: — Specialty: Oncology Objective: Adverse events of drug therapy Background: Enterocolitis is an immune-related adverse event associated with nivolumab treatment. Although intravenous corticosteroids and infliximab are recommended as a first-line and second-line therapy, respectively, there is no established treatment for severe enterocolitis that is refractory to these drugs. Case Report: A 62-year-old male with non-small cell lung cancer, with multiple brain metastasis, received nivolumab as the eighth-line chemotherapy for his disease. A few days after nivolumab administration, grade 2–3 enterocolitis developed in the patient. The enterocolitis improved to grade 1 after careful observation; however, it was aggravated to grade 3 after resuming nivolumab treatment. After cessation of nivolumab, 3.3 mg of intravenous dexamethasone and 40 mg of methylprednisolone were administered for 16 days and subsequently 30–60 mg of oral prednisolone was administered for 50 days, with little improvement in the patient’s colitis. A second-line treatment with 5 mg/kg of infliximab was twice attempted, but the patient had persistent diarrhea. Therefore, 50 mg of oral cyclosporine was started as a third-line therapy. Three days after the start of cyclosporine, the number of diarrhea events decreased, with resolution 2 weeks after cyclosporine administration. Conclusions: Oral cyclosporine treatment can be a third-line therapy for enterocolitis associated with immune-related adverse events.

Reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redox potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d °, of ion pairing. Values of ΔG d ° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.

A fluid material with high protein content (120–310 mg mL−1) was formed through the ordered self-assembly of native proteins segregated from water. This material is instantly prepared by the simple mixing of a protein solution with anionic and cationic surfactants. By changing the ratio of the surfactants based on the electrostatic characteristics of the target protein, we observed that the surfactants could function as a versatile molecular glue for protein assembly. Moreover, these protein assemblies could be disassembled back into an aqueous solution depending on the salt conditions. Owing to the water-retaining properties of the hydrophilic part of surfactants, the proteins in this material are in a water-rich environment, which maintains their native structure and function. The inclusion of water also provides functional extensibility to this material, as demonstrated by the preparation of an enzymatically active gel. We anticipate that the unique features of this material will permit the use of proteins not only in solution but also as elements of integrated functionalized materials.

Micro helical antennas whose resonance correspond to THz frequency region can be fabricated from biological algae spirulina via electroless metal coating. Radiation characteristics of the micro helical antenna are investigated by using THz near-field microscope. Both normal and end-fire mode radiations with different frequency characteristics can be successfully observed in real time.

Electron photoemission and ponderomotive acceleration by surface enhanced optical fields is considered as a plausible mechanism of terahertz radiation from metallic nanostructures under ultrafast laser excitation. To verify this mechanism, we studied experimentally terahertz emission from an array of gold nanorods illuminated by intense (~10–100 GW/cm2) femtosecond pulses of different central wavelengths (600, 720, 800, and 1500 nm). We found for the first time that the order of the dependence of the terahertz fluence on the laser intensity is, unexpectedly, almost the same (~4.5–4.8) for 720, 800, and 1500 nm and somewhat higher (~6.6) for 600 nm. The results are explained by tunneling currents driven by plasmonically enhanced laser field. In particular, the pump-intensity dependence of the terahertz fluence is more consistent with terahertz emission from the sub-cycle bursts of the tunneling current rather than with the ponderomotive mechanism.

Vibrational cooling was investigated in a set of homologous dimers and trimers with methyl viologen repeat units (MV2+). The rapid

The direct current (DC) motor is a rotary device that converts DC electrical energy into mechanical energy. However, it is known that, in downsizing the currently available macromotor, rotary motion of DC micromotors cannot work well due to the larger viscous effect. Here, we report simple DC micromotors working under a new principle. We previously revealed that in an oil phase containing an ionic surfactant, non-spherical particles exhibit various types of regular motions such as spinning and circular orbital motions. In this study, we found that a microhelix exhibits a new type of periodic motion, namely, the cork-screw-type rotation, in a specific direction depending on the material of the helix, metal or non-metallic organics. The results show that a left-handed nickel helix rotates in the clockwise direction when viewed from the positive electrode, whereas an organic one rotates in the opposite direction (anti-clockwise) under the same electrode arrangement with stationary constant DC voltage. In addition, we demonstrate that the cork-screw rotation is switched to opposite direction by changing the handedness (chirality). It is to be noted that the micromotors reported here maintain their stable motion without any mechanical support such as rotational axes or electronic switching devices. The invented DC micromotor would be applicable for mechanical and fluidic devices, being useful as a smart device in microrobots and microfluidics.

The controlled synthesis of multiarmed alternating thienylene–tetrafluorophenylene copolymers by the polymerization of 2-pentafluorophenyl-5-trimethylsilylthiophene under transition-metal-free conditions is demonstrated. The designed di- and trifunctional fluorosilicate initiators prepared by the reaction of 1,4- and 1,3-bis[(trimethylsilyl)ethynyl]benzene and 1,3,5-tris[(trimethylsilyl)ethynyl]benzene and tetrabutylammonium fluoride afford two-arm (I- and V-shaped) and three-arm (Y-shaped) polymers with controlled molecular weights and relatively low dispersities. The structures of the polymers were successfully confirmed using NMR spectroscopy.

The Lewis base-promoted alkynylation of fluorobenzenes using trimethylsilylacetylenes studying the reactivity as a function of the number of fluoride groups is described. The reaction of 1-(pentafluorophenyl)- and 1-(3,4,5-trifluorophenyl)-2-phenylacetylenes and 1-(4-methoxyphenyl)-2-trimethylsilylacetylene with CsF/18-crown-6 in DMSO gave the alkynylated products in moderate to good yields with high regioselectivity under mild conditions. However, the 3,4-difluorophenyl derivative showed low reactivity.

The orientation transition from perpendicular to parallel alignment of PEO cylindrical microdomains within PEO-b-PMA(Az) films has been demonstrated via introducing a small amount of polydimethylsiloxane (PDMS) into block copolymers (BCPs). The introduced PDMS can change the surface energy difference of the two blocks and induce a soft shearing force during the annealing process, which affects the alignment of PEO cylindrical domains synergically. With this understanding, the PDMS-assisted method can possibly be generalized to align a wide variety of other BCPs. The BCP films with controllable alignment can be used as lithographic nanotemplates to prepare nanowire arrays, which have enormous potential application in the field of integrated circuits.

A transition-metal-free polymerization of an AB-type monomer for the synthesis of well-defined poly(p-phenyleneethynylene)s is described. The polymerization of 1-pentafluorophenylethynyl-4-[(trimethylsilyl)ethynyl]benzene with a catalytic amount of tetrabutylammonium fluoride or potassium t-butoxide in the presence of cryptand[2.2.2] affords polymers within a few minutes. When monitoring the polymerization, the molecular weight as a function of monomer conversion shows a linear relationship, where the polydispersity indexes are around 1.6. The polymerization proceeds predominantly via intramolecular fluoride anion transfer to the polymer end. End capping of the active polymerization end is also demonstrated.

Ordered mesoporous crystalline titania with high thermal stability is directly synthesized in a simple one-pot procedure via an integrated approach of a solvent evaporation-induced self-assembly (EISA) technique and template-carbonization strategy by using a comb-like amphiphilic liquid crystal (LC) block copolymer (BCP) PEO-b-PMA(Az) with abundant sp2-carbons as a structure-directing agent. These BCP containing LC rigid segments with distinct hydrophilic/hydrophobic contrast can form robust micelles and co-assemble with titania sol into ordered mesostructures which are stable during the whole EISA process. Template carbonization in nitrogen after ageing is the key step to obtain the ordered crystalline mesostructures. The synthesized titania materials have a large pore size (∼4.87 nm) and pore volume (∼0.37 cm3 g−1) and high surface area (∼239 m2 g−1), as well as high thermal stability (>700 °C). Additionally, mesoporous titania shows good photocatalytic activity for the degradation of rhodamine B in an aqueous suspension due to its highly crystalline framework and large surface area. This simple, yet facile method can therefore be expanded to other ordered crystalline mesoporous materials through high-temperature heat treatments.

Protein-templated structured silica and titania are fabricated via a biomimetic method based on the synergistic effect of amine/carboxyl complexes under ambient conditions. Atelocollagen-templated silica showed a tangled fibrous structure with a smooth surface. The number of carboxyl groups of a protein is an important factor for homogeneous silica growth.

The design and synthesis of asymmetric AB-type monomers, 2-polyfluorophenyl-5-trimethylsilylthiophenes, and the transition-metal-free polymerization promoted by fluoride anions are described. The polymerization depended on the substitution position and also the number of fluorines on the phenyl groups; i.e., a 3,4,5-trifluorophenyl-substituted monomer proceeded the polymerization by a catalytic amount of potassium t-butoxide in the presence of cryptand[2.2.2] with controlled molecular weights and relatively low polydispersity indexes, but 2,4,6- and 2,3,4-trifluoro-substituted and also 3,4-difluoro-substituted monomers did not. The NMR spectra of the resulting polymers were consistent with a highly regulated structure for the polymer main chain, indicating that the polymerization process itself must be highly regioselective under these conditions. By using the polymerization, end-capping and block copolymerization with high fidelity were also demonstrated.

Asymmetric composite membranes with rectifying properties are developed by grafting pH-stimulus-responsive materials onto the top layer of the composite structure, which is prepared by two novel block copolymers using a phase-separation technique. This engineered asymmetric composite membrane shows potential applications in sensors, filtration, and nanofluidic devices.

We report unique self-assembled monolayers (SAMs) consisting of dendritic viologen-arranged molecules with an ω-mercaptodecyl group (An, n (dendritic generation) = 0–3) at the apex of the dendritic structure, which can accommodate a specific amount of metal anionic complexes defined by the dendritic structure. Dendritic molecules from several generations were successfully synthesized via microwave heating, thus providing easy access to third-generation molecules without requiring protection/deprotection processes during generation growth. SAMs of the dendritic molecules were fabricated by soaking gold substrates in solutions of the molecules in an acetonitrile/ethanol mixture at room temperature. Counter anions of the viologen units in the SAMs could be exchanged easily for various metal anionic complexes, such as PtCl42–, CuCl42–, and PdCl42–, by immersing the SAMs in aqueous solutions of the ions. X-ray photoelectron spectroscopy of the SAMs revealed that the amount of the metal anionic complexes accomm...

This paper describes the reversible control of the size of liquid-metal nanoparticles under ultrasonication. Gallium was utilized as a liquid metal, which has a melting point of 29.8 °C. Investigating the effects of ultrasonication (power, time, and temperature) on the formation of gallium nanoparticles revealed that the process is similar to the formation of oil in water (O/W) or water in oil (W/O) emulsions, as the temperature significantly affects the size of the gallium nanoparticles (GaNPs). Under ultrasonication, the balance between the break-up and coalescence of the GaNPs can be adjusted by changing the temperature or adding acid through modulating the natural surface oxide layer (which can be removed with acid) and the stabilizing effect of the surfactant dodecanethiol. Coalescence was predominant at higher temperatures, whereas particle break-up was found to be predominant at lower temperatures. Furthermore, the change in size was accompanied by a shift in the plasmonic absorption of the GaNPs in the UV region.

Pyrrole (Py) and thiophene derivatives were electropolymerized on a microphase-separated block copolymer [PEO-b-PMA(Az)] coated ITO electrode in order to form the corresponding conducting polymer nanostructures of perpendicularly oriented and hexagonally arranged cylinders as a template without the removal of one of the domains. Polypyrrole (PPy) nanowires grew through PEO cylindrical domains oriented perpendicular to the electrode to afford an array with an aspect ratio of up to 140 and a density of up to 4.4 × 1012 wires/in.2. Long, straight, π-stacked crystalline structures assigned to PPy main chains were observed in high-resolution TEM images of the individual wires. Additional elaborately crafted electropolymerization was demonstrated on a nanometer scale: (i) stepwise electropolymerization of Py and 3,4-ethylenedioxythiophene (EDOT) afforded segmented PPy–poly(3,4-ethylenedioxythiophene) (PEDOT) and PEDOT–PPy wires with nanoheterojunctions and (ii) one-pot electropolymerization of a mixture of Py a...

An amphiphilic liquid-crystalline block copolymer consisting of hydrophilic poly(4-vinylpyridine) (P4VP) and hydrophobic polymethacrylate with liquid-crystalline stilbene mesogens in the side chain (PMA(Stb)) was synthesized using reversible addition–fragmentation chain-transfer (RAFT) polymerization. The GISAXS and TEM measurements show that perpendicularly aligned P4VP cylinders are spontaneously formed in the PMA(Stb) matrix with a smectic layer of the liquid crystal through microphase separation.

A liquid crystalline block copolymer, composed of poly(ethylene oxide) (PEO) and polymethacrylate (PMA)-bearing azobenzene (Az) mesogen side chains, uniquely forms perpendicularly oriented PEO cylinders in a film on various substrates, independent of the substrate surface energy. In this paper, it is revealed that the perpendicular cylinders are formed at the air interface of the block copolymer film, as the perpendicular cylinders and liquid crystal structures were observed only in the vicinity of the air interface for a block copolymer film annealed for a short period of 5 s. On the basis of this mechanism of air-interface-induced perpendicular cylinder formation, we developed a surface covering method to prevent the perpendicular cylinder formation and instead induce parallel cylinder formation. Moreover, uniaxial cylinder films were fabricated by a combination of the surface covering and substrate rubbing methods. The surface covering layer for controlling cylinder orientation can be removed to utiliz...

Chemical epitaxy with a density multiplication process was applied to the perpendicularly oriented hexagonal cylinder nanostructure of liquid crystalline block copolymer (PEO-b-PMA(Az)) thin film through thermally induced microphase separation by using a newly designed PMA(Az)24 brush. The hexagonal lattice orientation with 1.9 tera-cylinders per inch2 was laterally controlled for long-range-ordered direct self-assembly. Furthermore, the direct pattern-transfer of the assembled structure to an Au nanodot array was demonstrated by doping of HAuCl4 selectively into the PEO cylindrical microdomains and then vacuum ultraviolet light irradiation to cause polymer etching and reduction of the Au ions.

A series of novel phthalocyanine (Pc)-tethered block copolymers, Pc-poly(methyl methacrylate)-block-polystyrene (Pc-PMMA-b-PS), with various molecular weights (number average molecular weight mass = 41, 66, 86 kg mol−1), were prepared by atom transfer radical polymerization and click chemistry. The structurally related Pc-tethered homopolymer, Pc-PMMA was also synthesized for comparison. Pc-PMMA forms homogeneous polymer films containing π-assemblies of the terminal Pc groups, whereas Pc-PMMA-b-PS self-assembles into a cylindrical morphology in which the Pc units show π–π interactions inside the confined PMMA cylinders. Such polymer designs have potential applications in optoelectronic devices.

A transition-metal-free controlled polymerization for the attainment of poly(p-aryleneethynylene)s is developed. The polymerization of 1-pentafluorophenyl-4-[(trimethylsilyl)ethynyl]benzene with a catalytic amount of fluoride anions proceeds in a chain-growth-like manner to afford polymers with controlled molecular weights and low polydispersity indexes. The mechanism involves a pentacoordinated fluorosilicate as a key intermediate. The anionic "living" nature of this process is applied to block copolymerization and also surface-terminated polymerization.

金沢大学先端科学・社会共創推進機構, With the advent of high volume manufacturing capabilities by extreme ultraviolet lithography, constant improvements in light source design and cost-efficiency are required. Currently, light intensity and conversion efficiency (CE) measurments are obtained by charged couple devices, faraday cups etc, but also phoshpor imaging plates (IPs) (BaFBr:Eu). IPs are sensitive to light and high-energy species, which is ideal for studying extreme ultraviolet (EUV) light from laser produced plasmas (LPPs). In this work, we used IPs to observe a large angular distribution (10°-90°). We ablated a tin target by high-energy lasers (1064 nm Nd:YAG, 1010 and 1011 W/cm2) to generate the EUV light. The europium ions in the IP were trapped in a higher energy state from exposure to EUV light and high-energy species. The light intensity was angular dependent; therefore excitation of the IP depends on the angle, and so highly informative about the LPP. We obtained high-space resolution (345 μm, 0.2°) angular distribution and grazing spectrometer (5-20 nm grate) data simultaneously at different target to IP distances (103 mm and 200 mm). Two laser systems and IP types (BAS-TR and BAS-SR) were also compared. The cosine fitting values from the IP data were used to calculate the CE to be 1.6% (SD ± 0.2) at 13.5 nm 2% bandwidth. Finally, a practical assessment of IPs and a damage issue are disclosed. © 2017 Author(s)., Embargo Period 12 months

Titanium oxide is known as a photocatalytic material that promotes the generation of hydrogen and oxygen from water by sunlight irradiation. In the present study, titanium oxide particles were treated by water jet cavitation generated using an ejector nozzle. Sub-stream suction occurs in small-sized high-pressure ejector nozzles because of the dynamic high pressure. The water containing titanium oxide powder or a mixed powder of titanium oxide and platinum enters the high-pressure water flow as a sub-stream. In the ejector nozzle, generation, growth, and collapse of cavitation are repeated with the particles of titanium oxide and platinum. Because the cavitation has an extremely high collapse pressure, the surface of the titanium oxide particles is processed by the microjets of cavitation in a so-called reactor comprising the ejector nozzle. The titanium oxide particles subjected to ejector cavitation (EC) processing were investigated for improvements to their photocatalytic properties under ultraviolet irradiation. It was found that noted that nano-level roughness is formed by EC processing. The TiO2 particles or TiO2 particles supported by Pt particles as a co- catalyst containing water were introduced into a vacuum chamber and the gases such as hydrogen and oxygen from the particle surfaces were measured by quadrupole mass spectrometry under ultraviolet irradiation. The EC processing was found to increase the amount of gases generated, including hydrogen and oxygen. Moreover, the amount of hydrogen in particular increases remarkably when both EC processing and support of platinum as a co-catalyst are used. It was also found that the titanium TiO2 particles were supporting minute platinum particles that detached from the original Pt particles during EC processing.

This work examines the polycondensation of 4-chloropyridine derivatives using an N -(4- tert -butylbenzyl)-4-chloropyridinium (BPymCl) initiator and ion exchange reagents NaBPh 4 , NaBF 4 , and TBABF 4 . The 1 H NMR spectra demonstrate that the product quantity is proportional to the total conversion of the monomer and the initiator. The MALDI-TOF MS spectrum shows that the product contains more than 9 monomer units. The polymerization was well-terminated via the addition of dimethylaminopyridine. These results indicate that the polycondensation proceeds in a chain-growth manner. This polycondensation could be a new example of a controlled polymerization with a well-defined end group.

A catalytic amount of fluoride anion promoted the polymerization of 2-pentafluorophenyl-5-trimethylsilylthiophene, providing a high-molecular-weight conjugated polymer in a chain-growth-like manner. The resulting polymer with a controlled molecular weight and a low molecular weight distribution was obtained in a high yield. The mechanism involves a pentacoordinated fluorosilicate as a key intermediate. The active polymerization end also initiated the second polymerization to afford well-defined block copolymers.

A series of amphiphilic liquid crystalline diblock copolymers, PEOm-b-PMA(Az)n, consisting of hydrophilic poly(ethylene oxide) and hydrophobic poly(methacrylate) moieties with side chains containing liquid crystalline (LC) azobenzene moieties, produced highly ordered microphase-separated films with PEO cylinders aligned perpendicular to the smectic LC layer of azobenzene in the PMA(Az) matrix. In this paper, morphological phase diagrams of PEOm-b-PMA(Az)n diblock copolymers above and below the isotropic transition temperature of LC azobenzene (Tiso) are presented. The diagrams are based on small-angle X-ray scattering (SAXS) measurements of approximately 70 kinds of polymers with varying degrees of polymerization in each block. An asymmetric phase diagram described against the volume fraction of PEO (fPEO) was obtained at temperatures above and below Tiso. The lamellar phase appears in the fPEO window 0.52 ≤ fPEO ≤ 0.78 above and below Tiso. Besides, the wide window, 0.087 ≤ fPEO < 0.52, allows the PEO cy...

We report a novel approach to slow the translocation of single-stranded DNA (ssDNA) by employing polyethylene oxide (PEO) filled nano-cylindrical domains as transportation channels. DNA strands were demonstrated to electrophoretically translocate through PEO filled cylindrical domains with diameters of 2 and 9 nm, which were self-assembled by amphiphilic liquid crystalline block copolymers. The average translocation rate of ssDNA strands was effectively reduced to an order of 10 μs per nucleotide, which was 1–2 orders slower than that attained by utilizing conventional solid-state nanopore devices.

Phase III clinical trials have comfirmed that the S-1 plus oxaliplatin(SOX)is inferior to the capecitabine plus oxaliplatin (COX)regimen in the treatment of metastatic colorectal cancer.On the basis of these findings, we compared, using a clinical decision analysis-based approach, the cost-effectiveness of the SOX and COX regimens.Herein, we simulated the expected effects and costs of the SOX and COX regimens using the markov model.Clinical data were obtained from Hong's 2012 report.The cost data comprised the costs for pharmacist labor, material, inspection, and treatment for adverse event, as well as the total cost of care at the advanced stage.The result showed that the expected cost of the SOX and COX regimen was 1,538,330 yen, and 1,429,596 yen, respectively, with an expected survival rate of 29.18 months, and 28.63 months, respectively.The incremental cost-effectiveness ratio of the SOX regimen was 197,698 yen/month; thus, the SOX regimen was found to be more cost-effective that the COX regimen.

Spirulina-templated metal μ coils (STMμC) are interesting materials for a wide range of terahertz (THz) applications due to their distinctive interactions with THz-light. We measured inclusive Mueller matrices of randomly distributed and one-dimensional (1D) STMμC-embedded paraffin sheets using Stokes polarimetry at 1.6 THz, where strong optical activity has already been reported. We demonstrated that the one-dimensional STMμC paraffin sheet can simultaneously express five polarization effects including linear-birefringence, linear-dichroism, circular-birefringence, circular-dichroism, and depolarization. Hence, STMμC can potentially be utilized for the control of various polarization phenomena of THz-light.

Inorganic semiconductor nanorods are regarded as the primary components of optical and electrical nanoscale devices. In this paper, we demonstrate the unidirectional alignment of monolayered and dispersed ZnO nanorods on a rubbed polyimide alignment layer, which was achieved by a conventional liquid crystal alignment technique. The outermost surfaces of the ZnO nanorods (average diameter 7 nm; length 50 nm) were modified by polymerization initiator moieties, and nematic liquid crystalline (LC) methacrylate polymers were grown by atom transfer radical polymerization. By regulating the densities of the polymerization initiator moieties, we successfully hybridized LC-polymer-grafted ZnO nanorods and small nematic LC molecules. The LC-polymer-modified ZnO nanorods were hierarchically aligned on the substrate via cooperative molecular interactions among the liquid crystal mesogens, which induced molecular orientation on the rubbed polyimide alignment layer.

A full-spectrum visible-light-responsive organophotocatalyst membrane array is designed and employed for a one-pass-flow water purification system. Whereas previous photocatalyst systems required s...

Highly ordered nanopore arrays were successfully fabricated using poly(ethylene oxide) (PEO) and polymethacrylate with azobenzene mesogen in side chains [PMA(Az)] block copolymer film based on irradiation of 172-nm vacuum ultraviolet (VUV) light. The block copolymer forms a highly ordered microphase-separated film with perpendicularly oriented PEO cylinders just by thermal annealing through a self-assembling process. We found that the etching rate of the PEO homopolymer was much higher than that of the PMA(Az) homopolymer at a chamber pressure of 102 Pa of atmosphere under VUV irradiation. The etching rate of the PEO component in the two systems of microphase separation and macrophase separation of the homopolymer blend crucially depended on the feature size of phase separation. In the PEO selective etching process of the block copolymer film, the water-contact angle of the film dramatically increased due to elimination of hydrophilic PEO. The resulting nanopore array film will be useful for low-density target materials.