Total synthesis of (S)-(+)-ent-phomapyrones B and surugapyrone B

Phomapyrone B ( 1 ), the 2-pyrones isolated from the phytopathogenic fungus Leptosphaeria maculans, has been synthesized as the enantiomeric form starting from (S)-2-methylbutanol ( 4 ). Surugapyrone B ( 3 ) isolated from Streptmyces sp. USF-6280 as an antioxidant has also been synthesized as a natural form. The absolute configuration of phomapyrone B ( 1 ) was estimated to be the (R)-form and that of surugapyrone B ( 3 ) being the (S)-form. A series of 2-pyrone derivatives 17 have been synthesized through the established procedure and their DPPH radical-scavenging activities have also been evaluated.     

Structure and properties of new olefin polymers

The relationship between molecular structures and physical properties of linear low density polyethylenes (LLDPEs) produced with single-site catalyst (SSC) was investigated. SSC polymerized LLDPE have excellent physical properties corresponding to its homogeneous molecular structure that had never been achieved by conventional Ziegler-Natta catalysts. It was found that some SSCs have the capability to produce LLDPEs with narrow molecular weight distribution but excellent melt properties. This result suggests that there exist long chain branches in these LLDPEs.     

Boosting Hydrogen Evolution at Visible Light Wavelengths by Using a Photocathode with Modal Strong Coupling between Plasmons and a Fabry-Pérot Nanocavity

Hot-hole injection from plasmonic metal nanoparticles to the valence band of p-type semiconductors and reduction by hot electrons should be improved for efficient and tuneable reduction to obtain beneficial chemical compounds. We employed the concept of modal strong coupling between plasmons and a Fabry-Pérot (FP) nanocavity to enhance the hot-hole injection efficiency. We fabricated a photocathode composed of gold nanoparticles (Au−NPs), p-type nickel oxide (NiO), and a platinum film (Pt film) (ANP). The ANP structure absorbs visible light over a broad wavelength range from 500 nm to 850 nm via hybrid modes based on the modal strong coupling between the plasmons of Au−NPs and the FP nanocavity of NiO on a Pt film. All wavelength regions of the hybrid modes of the modal strong coupling system promoted hot-hole injection from the Au−NPs to NiO and proton/water reduction by hot electrons. The incident photon-to-current efficiency based on H₂ evolution through water/proton reduction by hot electrons reached 0.2 % at 650 nm and 0.04 % at 800 nm.     

Simple separation of isomeric sialylated N-glycopeptides by a zwitterionic type of hydrophilic interaction chromatography

Asparagine-linked oligosaccharides (N-glycans) usually show structural heterogeneity, especially in proteins with sialylated N-glycans and, therefore, their structural analysis is still very difficult. A zwitterionic type of hydrophilic interaction chromatography column with sulfobetaine functional groups (called a ZIC-HILIC column) was applied to the separation of tryptic peptides of alpha-1-acid glycoprotein. It was demonstrated that the ZIC-HILIC separation column has a selectivity for sialylated N-glycopeptides and a high capability for separation based on the structural recognition of sialylated N-glycan isomers as well as for the previously reported neutral N-glycans and N-glycopeptides. The retention characteristics of neutral and sialylated N-glycans derivatized with 2-aminopyridine (PA N-glycans) demonstrate that the retentions of the N-glycans are based primarily on hydrophilic interaction with the water-rich liquid layer generated on the surface of the ZIC-HILIC column. In addition, the electrostatic repulsion interaction shielded with counter ions effectively tunes the separation and recognition of sialylated N-glycan isomers.     

Two-dimensional hydrophilic interaction chromatography coupling anion-exchange and hydrophilic interaction columns for separation of 2-pyridylamino derivatives of neutral and sialylated N-glycans

A novel chromatographic approach coupling anion-exchange (diethylaminoethylene) and hydrophilic-interaction (amide or zwitterionic type) columns was developed for the separating of 2-pyridylamino derivatives of N-glycans (PA-N-glycans). This is a kind of on-line, two-dimensional (2D) separation approach in hydrophilic-interaction chromatography (called the 2D-HILIC method), analogous to that of coupling cation- (or anion-, or mixed ion-) exchange and reversed-phase columns in hydrophobic interaction (reversed-phase) chromatography. The efficiency of the 2D-HILIC method was tested with biantennary neutral and sialylated PA-N-glycan standards by properly combining linear gradient elutions of water-acetonitrile and spiked-salt (ammonium acetate) elutions. The retention time RSDs of all the peaks in three sequential runs of a 100 min cycle are less than 0.52%, which indicates a reasonably good repeatability of the 2D-HILIC method. Then, the method was applied to a complex mixture of PA-N-glycans from human serum proteins. It was demonstrated that the neutral PA-N-glycans and mono-, di-, tri-, and tetrasialylated PA-N-glycans are able to be eluted in turn according to the number of sialic acids in an automated (programmed) single run.     

电子封装、QFP和MCM热变形的实验及数值分析

0Introduction Anelectronicpackageisgenerallyconstructedwithanactivesiliconchip,mountisland,gold wires,leadframesandsoldersasshowninFig.1(a).Toprotectfromtheenvironment,thesilicon chipisusuallyencapsulatedinresin.SincethesematerialshavedifferentCTE(coeffic…     

Enhancement in age hardenability of sintered Ti–5Fe alloy by Zr addition processed by pulsed electric current sintering

The age-hardenable Ti–5Fe–5Zr (wt. %, 5Zr) alloy has been consolidated by pulsed electric current sintering, following a β solution treatment, and the results are compared with a Ti–5Fe (0Zr) alloy. The precipitation sequence measured at 640°C ageing is β?+?athermal ω?→?β?+?isothermal ω?→?β?+?α. At the peak hardness isothermal ω phase forms at 20?s of ageing. The Zr addition retards the precipitation kinetics of the α phase; as a result, the α phase nucleates at latest at 300?s ageing in the overaged state. Fe is partitioned into β, while it is depleted from the α phases. There is Zr enrichment near the α/β interface when the α phase precipitates due to a solute drag effect; the growth rate of the α phase in the 5Zr alloy is significantly reduced compared with that in the 0Zr alloy.     

An electrically conductive metallocycle: densely packed molecular hexagons with π-stacked radicals

Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni₆(NDI-Hpz)₆(dma)₁₂(NO₃)₆]·5DMA·nH₂O (PMC-hexagon) (NDI-Hpz = N,N′-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of H₂O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2–2.1) × 10⁻⁴ S cm⁻¹ (pressed pellet), which is superior to that of most NDI-based conductors including metal–organic frameworks and organic crystals. These findings open up the use of metallocycles as building blocks for fabricating conductive porous molecular materials.

Intrinsically electron-conductive metallocycle was synthesized. π-Radicals play a key role in constructing π-stacked columns among molecular hexagons and achieving high electrical conductivity over 10⁻⁴ S cm⁻¹ in polycrystalline pellet.     

Analysis of the number of hydrogen bond groups of a multiwalled carbon nanotube probe tip for chemical force microscopy

In this paper, we describe a statistical method of quantification of the number of functional groups at the contact area of a probe tip for atomic force microscopy from the result of repetitive pull-off force measurements. We have investigated laboratory-made carbon nanotube (CNT) probe tips to apply them for chemical force microscopy because limited number of functional groups at the tip-end is expected. Using a CNT tip, we conducted repetitive pull-off force measurements against a self-assembled monolayer terminated with carboxyl group and analyzed them in terms of the number of hydrogen bond groups at the CNT tip. The elementary hydrogen bond rupture force quantum in n-decane medium was estimated to be 84.2 ± 0.5 pN in the present system. Thus it was revealed that only a couple of hydrogen bond groups of the CNT tip were participating in hydrogen bonding with the sample on an average in this experimental system.