一种经氟化和热处理在双壁碳纳米管上生成缺陷的方法(英文)

Nanoscale defects in the outer tube to preserve the electrical and optical features of the inner tube can be engineered to exploit the intrinsic properties of double walled carbon nanotubes (DWCNTs) for various promising applications. We demonstrated a selective way to make defects in the outer tube by the fluorination of DWCNTs followed by the thermal detachment of the F atoms at 1000 °C in argon. Fluorinated DWCNTs with different amounts of F atoms were prepared by reacting with fluorine gas at 25, 200, and 400 °C that gave the stoichiometry of CF0.20, CF0.30, and CF0.43, respectively. At the three different temperatures used, we observed preservation of the coaxial morphology in the fluorinated DWCNTs. For the DWCNTs fluorinated at 25 and 200 °C, the strong radial breathing modes (RBMs) of the inner tube and weakened RBMs of the outer tube indicated selective fluorine attachment onto the outer tube. However, the disappearance of the RBMs in the Raman spectrum of the DWCNTs fluorinated at 400 °C showed the introduction of F atoms onto both inner and outer tubes. There was no significant change in the morphology and optical properties when the DWCNTs fluorinated at 25 and 200 °C were thermally treated at 1000 °C in argon. However, in the case of the DWCNTs fluorinated at 400 °C, the recovery of strong RBMs from the inner tube and weakened RBMs from the outer tube indicated the selective introduction of substantial defects on the outer tube while preserving the original tubular shape. The thermal detachment of F atoms from fluorinated DWCNTs is an efficient way to make highly defective outer tubes for preserving the electrical conduction and optical activity of the inner tubes.     

Expression and Characterization of Recombinant GH11 Xylanase from Thermotolerant Streptomyces sp. SWU10

Xylans are major hemicellulose components of plant cell wall which can be hydrolyzed by xylanolytic enzymes. Three forms of endo-β-1,4-xylanases (XynSW1, XynSW2A, and XynSW2B) produced by thermotolerant Streptomyces sp. SWU10 have been reported. In the present study, we described the expression and characterization of the fourth xylanase enzyme from this bacteria, termed XynSW3. The gene containing 726 bp was cloned and expressed in Escherichia coli. The recombinant enzyme (rXynSW3) was purified from cell-free extract to homogeneity using Ni-affinity column chromatography. The apparent molecular mass of rXynSW3 was 48 kDa. Amino acid sequence analysis revealed that it belonged to a xylanase of glycoside hydrolase family 11. The optimum pH and temperature for enzyme activity were 5.5–6.5 and 50 °C, respectively. The enzyme was stable up to 40 °C and in wide pH ranges (pH 0.6–10.3). Xylan without arabinosyl side chain is the most preferable substrate for the enzyme. By using birch wood xylan as substrate, rXynSW3 produced several oligosaccharides in the initial stage of hydrolysis, and their levels increased with time, demonstrating that the enzyme is an endo-acting enzyme. The major products were xylobiose, triose, and tetraose. The rXynSW3 can be applied in several industries such as food, textile, and biofuel industries, and waste treatment.     

Enhanced collective optical response of vast numbers of silver nanoparticles assembled on a microbead

We investigated the optical response of a huge number of silver nanoparticles (AgNPs) densely assembled on an organic microsphere, i.e., AgNP-fixed bead, under the collective phenomena of localized surface plasmons. For this purpose, various optical properties of such a AgNP-fixed bead were analyzed in aqueous solution by dark-field optical microscopy and laser Raman microscopy. In particular, in comparison with the optical spectrum of single AgNPs, significant spectral broadening and redshift were observed due to plasmonic superradiance with decreasing interparticle distance to the subnanoscale when using small binder molecules in the AgNP-fixed bead. Furthermore, we observed surface-enhanced Raman scattering and clarified the sensitivity of the signal intensity to the size of the binder molecules between the AgNPs, which can be explained based on optical response theory using a discrete integral with spherical cells. These results and discussion provide a guiding principle for broadband plasmonic light absorbers and for highly sensitive detection of small molecules and nanoscale biomaterials based on vast numbers of nanogaps produced by a bottom-up self-assembly process.     

The electronic band structure analysis of OLED device by means of in situ LEIPS and UPS combined with GCIB

Low-energy inverse photoelectron spectroscopy (LEIPS) and ultraviolet photoelectron spectroscopy (UPS) incorporated into the multitechnique XPS system were used to probe the ionization potential and the electron affinity of organic materials, respectively. By utilizing gas cluster ion beam (GCIB), in situ analyses and depth profiling of LEIPS and UPS were also demonstrated. The band structures of the 10-nm-thick buckminsterfullerene (C₆₀) thin film on Au (100 nm)/indium tin oxide (100 nm)/glass substrate were successfully evaluated in depth direction.     

Infrared-A Irradiation-induced Inhibition of Human Keratinocyte Proliferation and Potential Mechanisms

Infrared-A (IRA), which can penetrate deeply into the human skin, is a major component of solar radiation and is recognized to promote photoaging of human dermis. To our knowledge, however, the cellular and molecular consequences of human epidermis exposure to IRA have not been clarified. Thus, we investigated whether IRA inhibits the proliferation of normal human epidermal keratinocytes (NHEKs). IRA irradiation ed in cell cycle arrest at G1 and a dose-dependent reduction in the proliferation of NHEKs. We found that mechanistic target of rapamycin complex 1 (mTORC1) was initially inactivated during IRA irradiation due to the formation of stress granules (SGs), and this inactivation was maintained for at least 6 h after irradiation due to Akt dephosphorylation. Furthermore, repeated exposure of human skin equivalents to IRA led to marked thinning of the epidermal cell layer. In conclusion, IRA irradiation inhibits mTORC1 activity possibly through two molecular mechanisms involving SG formation in the early-phase and subsequent Akt dephosphorylation. This sequential mechanism seems to cause G1 cell cycle arrest and a reduction in cell proliferation, supporting the hypothesis that the decreased proliferation of basal keratinocytes that occurs during skin aging might be partly attributable to IRA radiation.     

Strong,Self-Healable,and Recyclable Visible-Light-Responsive Hydrogel Actuators

The most pressing challenges for light-driven hydrogel actuators include reliance on UV light, slow response, poor mechanical properties, and limited functionalities. Now, a supramolecular design strategy is used to address these issues. Key is the use of a benzylimine-functionalized anthracene group, which red-shifts the absorption into the visible region and also stabilizes the supramolecular network through π–π interactions. Acid–ether hydrogen bonds are incorporated for energy dissipation under mechanical deformation and maintaining hydrophilicity of the network. This double-crosslinked supramolecular hydrogel developed via a simple synthesis exhibits a unique combination of high strength, rapid self-healing, and fast visible-light-driven shape morphing both in the wet and dry state. As all of the interactions are dynamic, the design enables the structures to be recycled and reprogrammed into different 3D objects.     

Flapping Peryleneimide as a Fluorogenic Dye with High Photostability and Strong Visible‐Light Absorption

Flapping fluorophores (FLAP) with a flexible 8π ring are rapidly gaining attention as a versatile photofunctional system. Here we report a highly photostable “flapping peryleneimide” with an unprecedented fluorogenic mechanism based on a bent‐to‐planar conformational change in the S₁ excited state. The S₁ planarization induces an electronic configurational switch, almost quenching the inherent fluorescence (FL) of the peryleneimide moieties. However, the FL quantum yield is remarkably improved with a prolonged lifetime upon a slight environmental change. This fluorogenic function is realized by sensitive π‐conjugation design, as a more π‐expanded analogue does not show the planarization dynamics. With strong visible‐light absorption, the FL lifetime response synchronized with the flexible flapping motion is useful for the latest optical techniques such as FL lifetime imaging microscopy (FLIM).     

Half‐Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation

Synthesis and deprotonation reactions of half‐sandwich iridium complexes bearing a vicinal dioxime ligand were studied. Treatment of [{Cp*IrCl(μ‐Cl)}₂] (Cp*=η⁵‐C₅Me₅) with dimethylglyoxime (LH₂) at an Ir:LH₂ ratio of 1:1 afforded the cationic dioxime iridium complex [Cp*IrCl(LH₂)]Cl ( 1 ). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oxime–oximato complex [Cp*IrCl(LH)] ( 2 ) and the anionic dioximato(2?) complex K[Cp*IrCl(L)] ( 3 ) sequentially. Meanwhile, twofold deprotonation of the sulfato complex [Cp*Ir(SO₄)(LH₂)] ( 4 ) resulted in the formation of the oximato‐bridged dinuclear complex [{Cp*Ir(μ‐L)}₂] ( 5 ). X‐ray analyses disclosed their supramolecular structures with one‐dimensional infinite chain ( 1 and 2 ), hexagonal open channels ( 3 ), and a tetrameric rhomboid ( 4 ) featuring multiple intermolecular hydrogen bonds and electrostatic interactions.     

Development of primary standard gas mixtures containing 10 µmol/mol oxygen in nitrogen with verification by a two-oven GC-TCD system for effective separation of oxygen from argon in presence of plenty of nitrogen

Accreditation and Quality Assurance - Primary standard gas mixtures (PSMs) containing 10 µmol/mol oxygen in nitrogen were prepared in aluminum alloy cylinders from pure nitrogen and...