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Using a newly developed edge-support heat treatment method of polyimide, self-standing graphite thin films (GTFs) with a frame were prepared. The graphite basal plane in the GTF was oriented in the direction of the film surface, resulting in GTFs with high quality, large area, and a uniform thickness of 50–120 nm. The thickness distribution (3σ) with an area of 25 mm × 25 mm and a thickness of 54 nm sample was 5.17 nm (measurement area 7.8 mm × 10.4 mm). The electric conductivity of a similarly prepared sample was 1.81 × 104 S/cm. The Young's modulus and ultimate tensile strength of a 60-nm-thick GTF were 1.02 × 102 and 5.34 GPa, respectively. Approximately 50 nm thick GTF samples were thinned by reactive ion etching using oxygen to fabricate a thickness between 10 and 20 nm. A film with an area of 10 mm × 10 mm and thickness of 16.7 nm exhibited a 3σ value of 1.80 nm which means that the thickness difference corresponds to 5 layers of graphite. The conductivity of a 16.2-nm-thick GTF was 1.79 × 104 S/cm. These results indicate that the etching proceeded uniformly. The proposed top-down method is an industrially superior method that overcomes the drawbacks of conventional bottom-up methods.

We have developed large-area, high-quality graphite thin films that are 0.5–3 μm thick. To prepare the graphite films, we used pyrolysis and graphitization of polyimide up to temperatures in the range 2900 °C-3300 °C, which is applicable to industrial-production processing. Given that the graphite layers of the films are highly oriented in the surface plane, they have good physical properties. The resulting electrical conductivity of graphite film of thickness 1.4 μm and area 10 × 10 cm2 that was treated at 3200 °C is 24,800 S/cm, and the electrical conductivity showed metallic temperature dependence. The carrier mobility of the film is 11,700 V/cm2, and the carrier concentrations of electrons (Ne) and holes (Nh) are 6.98 × 1018 cm−3 and 5.90 × 1018 cm−3, respectively. We consider the high electrical conductivity and mobility to have been derived from the homogeneous, highly oriented graphite layers. We found that graphitization of films less than 3 μm thick progresses uniformly throughout the film, and the resulting graphite films have structures with uniform, highly oriented layers. The produced graphite thin films have excellent physical properties and can be easily handled, so we believe that many industrial applications are possible.

Multilayer graphene sheets were prepared by heat treatment of polyimide films at temperatures of up to 3000 °C. The sheets consist of highly oriented graphite layers with excellent mechanical robustness and flexibility. Key features of these sheets include their high thermal conductivity in the in-plane direction, good mechanical properties, and high carbon purity. The results suggest that the multilayer graphene sheets have great potential for charge stripping foils that persist even under the highest ion beam intensities irradiation and can be used for accelerator applications.

High-density highly oriented graphite sheets provided by Kaneka Corporation have been applied as stripper disks for heavy-ion acceleration at RIKEN RI Beam Factory since 2014. The graphite sheets withstand increasing amounts of beam intensity. We observed the graphite sheets after beam irradiation with an electron microscope and their lifetime was discussed.

Photolyses of thianthrene sulfilimine derivatives in the presence of several olefins were studied and found to afford the corresponding aziridines in good yields, particularly, in case of 2,8-dibromo-[5-(N-tosyl)imino]thianthrene. This reaction was considered to proceed via generation of nitrene by photolytic S–N bond cleavage of thianthrene sulfilimines. Further, photo-aziridination of olefins by thianthrene sulfilimine derivatives was intensively studied to make clear the ability as nitrene precursors.

Several 1- and 2-substituted thianthrene sulfilimine derivatives were prepared and the selectivity toward oxidation and N-tosylimination under several conditions was studied. In the photolysis of trans-5-(N-p-tosyl)iminothianthrene 10-oxide (trans-10), photo isomerization to cis-10 was observed. Further, photoimino-transfer reaction of sulfilimines and their 10-mono- and -dioxide derivatives to sulfides was intensively studied to make clear the ability as nitrene precursors.

Cytoplasmic peptide:N-glycanase (PNGase) is an enzyme that removes N-glycans from misfolded glycoproteins. The function of cytoplasmic PNGase plays a significant role in the degradation of misfolded glycoproteins, which is critical for cell viability. Recently, we reported that haloacetoamidyl derivatives of high-mannose-type oligosaccharides selectively modify the catalytic cysteine of cytoplasmic PNGase and serve as its specific inhibitor. Interestingly, a drastically simplified chloroacetamidyl chitobiose derivative [(GlcNAc)(2)-ClAc] was also reactive to PNGase. In our work, it was conjugated to a hydrophobic fluorophore in order to render (GlcNAc)(2)-ClAc cells permeable. We demonstrated that this compound [BODIPY-(GlcNAc)(2)-ClAc] specifically binds to cytoplasmic PNGase from budding yeast (Png1). To date, only Z-VAD-fmk is known as an inhibitor of PNGase. BODIPY-(GlcNAc)(2)-ClAc and Z-VAD-fmk share the same binding site on Png1, while BODIPY-(GlcNAc)(2)-ClAc has markedly stronger inhibitory activity. The functional analysis of PNGase using Z-VAD-fmk should be carefully interpreted because of its intrinsic property as a caspase inhibitor. In sharp contrast, chloroacetamidyl chitobiose was not reactive to caspase. In addition, BODIPY-(GlcNAc)(2)-ClAc did not bind either chitobiose-binding lectins or PNGase from other sources. Moreover, fluorescent microscopy clearly showed that BODIPY-(GlcNAc)(2)-ClAc was efficiently introduced into cells. These results suggest that this compound could be an in vivo inhibitor of cytoplasmic PNGase.

Every year, more than 50,000 people in subtropical and tropical regions suffer from ciguatera seafood poisoning. The extremely low level of the causative neurotoxins (ciguatoxins) in fish has hampered the preparation of antibodies for detection of the toxins. In this study, we produced a monoclonal antibody (8H4) against the right end of ciguatoxin CTX1B (1) and 51-hydroxyCTX3C (3) by immunizing mice with the keyhole limpet hemocyanin-conjugate of the synthetic HIJKLM ring fragment (10). We used 8H4 and another previously reported monoclonal antibody (10C9) that recognizes the left end of 3 to develop a sandwich enzyme-linked immunosorbent assay (ELISA) to detect 3. The assay could detect 3 down to the ppb level and lacked cross-reactivity with other related marine toxins, including brevetoxin A, brevetoxin B, okadaic acid, and maitotoxin.

Systematic synthesis of high-mannose-type sugar chains of asparagine-linked glycoproteins is described. To construct the target sugar chains, we employed the convergent route, using three oligosaccharide components, the common hexasaccharide, branched tri-, tetra- and pentasaccharides, and mono-, di-, and triglucosyl fragments. Construction of the β-mannoside linkage was performed using p -methoxybenzyl-assisted intramolecular aglycon delivery. The hexasaccharide fragment was coupled with the branched mannooligosaccharide donors such as M5, M4B, M4C, and M3 to give undecasaccharide (M9), decasaccharide (M8B and M8C), and nonasaccharide (M7), respectively. Incorporation of mono-, di-, and triglucosyl fragments toward them gave tetradecasaccharide (G3M9), tridecasaccharide (G2M9), dodecasaccharide (G1M9), undecasaccharide (G1M8B and G1M8C), and decasaccharide (G1M7), respectively.

The right wings (13 and 14) of ciguatoxins were synthesized highly stereoselectively. Key transformations in the synthesis are (i) an oxiranyl anion strategy to attach the H ring, (ii) intramolecular carbonyl olefination to cyclize the J ring, (iii) regio- and stereoselective reduction of the epoxyacetal to install the C42-stereocenter, and (iv) stereoselective reductive etherification to construct the K ring. The present procedure greatly improved the stereoselectivity and efficiency in comparison to a previous synthesis. Remarkably, only 23 steps were required from monocyclic I ring 5 to construct the ciguatoxin right wings. The high practicality of the present synthesis ensures a sufficient supply of these complex fragments for total syntheses and biomedical applications.

A concise route to the HIJKLM-ring fragment 10 of ciguatoxin (CTX) and 51-hydroxyCTX3C was developed in which oxiranyl anion addition and intramolecular carbonyl olefination were utilized as key transformations. The present procedure requires only 23 steps from the I-ring 5, while 35 steps were employed in a previous synthesis of the corresponding right wing 11 of CTX3C. The high efficiency of the present synthesis ensures a supply of 10 for total synthesis and biomedical applications.

Ciguatoxins, the principal causative toxins of ciguatera seafood poisoning, are large ladder-like polycyclic ethers with the 13 ether rings ranging from five- to nine-membered. In this paper, we describe the total synthesis of the two most toxic members of the ciguatoxin family, ciguatoxin 1 and 51-hydroxyCTX3C 2, based on a unified synthetic strategy. The key features in our syntheses were (i) direct construction of the O,S-acetal from the corresponding left and right wing fragments (3, 4, 14); (ii) stereo- and chemoselective radical reaction of the alpha-oxyradical with pentafluorophenyl acrylate to achieve cyclization of the seven-membered G-ring; (iii) ring-closing metathesis reaction to build the nine-membered F-ring; and (iv) an efficient protective group strategy using the oxidatively removable 2-naphthylmethyl groups.

To evaluate the ability of dibenzothiophene N-substituted sulfilimines as photochemical nitrene sources, their photolyses in the presence of several trapping reagents, such as sulfides, olefins, and phosphorus compounds, were performed. In the reactions, the corresponding imino-transfer compounds, namely sulfilimines, aziridines, and iminophosphoranes, were formed in good yields, indicating dibenzothiophene N-tosyl and N-acylsulfilimines have a potent nature as nitrogen sources.

Calreticulin (CRT) is a soluble molecular chaperone of the endoplasmic reticulum. It is a lectin that promotes the folding of proteins carrying N-linked glycans. Recent investigations have revealed that glucosylated high-mannose-type glycans are employed as key elements in this process. Here, we performed quantitative analyses of the interaction of CRT with various disaccharides, including fluorine-substituted analogues using a quartz-crystal microbalance (QCM). These experiments revealed the weak affinity of 2- and 3-fluoroglucose derivatives. On the other hand, 6-fluoroglucose derivatives exhibited a significant affinity, indicating that the role of 6-position of OH is less significant for binding to CRT. We also characterized binding epitope of the Glcalpha1-3Man(alpha)Me to CRT by saturation transfer difference (STD) NMR spectroscopy. It is proposed that 2-, 3-, and 4-positions of Glc and 3-, 4-, and 6-positions of Man are in close contact with CRT binding pocket, while 6-position of Glc and 2-position of Man are not. These finding are in excellent agreement with our QCM experiment.