Synthetic study of kosinostatin aglycone: synthesis of BCDE rings using alkoxycarbonylmethylation of diazonaphthoquinone

A synthetic study of kosinostatin aglycone is reported. Synthesis of key intermediate lactone 3, which corresponds to the BCDE ring fragment, was accomplished, and the precursor BCD ring fragment 5 was synthesized via two routes. First, 5 was synthesized from 2,5-dimethoxybenzaldehyde 16 by the combination of typical known transformations including efficient application of non-aqueous OsO₄ oxidation in the presence of PhB(OH)₂. However the synthesis required 15 long steps, and its main difficulty was ortho-alkoxycarbonylmethylation of 1-naphthol. Next we attempted to apply our recently developed alkoxycarbonylmethylation of diazonaphthoquinone for the synthesis of 5, and 5 was successfully synthesized in 9 steps from the same starting compound 16. Finally, 5 was stereoselectively converted to lactone 3 via trifluoroacetic acid-mediated cyclization of the 3,4-epoxycylohexanecarboxylic acid derivative.     

Synthesis of 3′-allylindoline spirobenzopyrans derived from 3-allyl-3H-indoles

In this study, 8 new spirobenzopyrans were synthesized. A novel, three-step, facile route for the synthesis of 3′-allylindoline spirobenzopyrans via 3-allyl-3H-indoles was developed. The newly synthesized spirobenzopyrans were evaluated for their photochromic properties. The presence of an allyl moiety at the 3′ position did not disturb the photochromic response. The steric effects of the diallyl groups at the 3′ position affected the interconversion between colored and colorless forms. Therefore, the allyl chain in 3′-allylindoline spirobenzopyrans can be utilized to attach these compounds to a molecular matrix. Consequently, this synthetic methodology could be readily applied to the creation of new photo-switchable materials.     

Effects of substrate and transfer on CVD-grown graphene over sapphire-induced Cu films

We differentiated the effects of Cu films deposited on single crystalline a-,r-,and c-plane sapphire substrates upon graphene films synthesized with atmospheric pressure chemical vapor deposition(CVD).The data illustrate that the realization of high-crystalline Cu film is dependent not only on the crystallinity of underlying substrate,but also on the symmetric match of crystallographic geometry between metal film and substrate.We also systematically investigated the effects of PMMA removal on the Raman ID/IG and IG/I2D values of transferred graphene.The results reveal that different PMMA removal methods do not alter the ID/IG values;instead,the residue of PMMA increases the IG/I2D values and the thermal decomposition of PMMA leads to higher IG/I2D values than the removal of PMMA with acetone.The effects of PMMA removal on variations of the Raman spectra are also discussed.     

Dibenzo[a,f]perylene Bisimide: Effects of Introducing Two Fused Rings

Perylene bisimides (PBIs) are fascinating dyes with various potential applications. To study the effects of introducing a dibenzo‐fused structure to the perylene moiety, π‐extended PBI derivatives with a dibenzo‐fused structure at both of the a and f bonds were synthesized. The twisted structure was characterized by X‐ray crystal structure analysis. In the cyclic voltammograms, the dibenzo[a,f]‐fused PBI showed a reversible oxidation wave at much less positive potential, relative to a dibenzo[a,o]‐fused PBI derivative. These data indicated that two ring fusions at both sides of a naphthalene moiety, which construct a tetracene core, effectively raise the HOMO level compared to fusion of one ring at each naphthalene moiety (two anthracene cores). The dibenzo[a,f]‐fused PBI derivative showed an absorption band at 735 nm with a shoulder band reaching 900 nm.     

Quantification of Intracellular Thiols by HPLC-Fluorescence Detection

Biothiols, such as cysteine and glutathione, play important roles in various intracellular reactions represented by the redox equilibrium against oxidative stress. In this study, a method for intracellular thiol quantification using HPLC-fluorescence detection was developed. Thiols were derivatized with a thiol-specific fluorescence derivatization reagent, viz. ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F), followed by reversed-phase separation on an InertSustain AQ-C18 column. Six different SBD-thiols (homocysteine, cysteine, cysteinylglycine, γ-glutamylcysteine, glutathione, and N-acetylcysteine as an internal standard) were separated within 30 min using a citric buffer (pH 3.0)/MeOH mobile phase. The calibration curves of all the SBD-thiols had strong linearity (R² > 0.999). Using this developed method, the thiol concentrations of human chronic myelogenous leukemia K562 cell samples were found to be 5.5–153 pmol/1 × 10⁶ cells. The time-dependent effect of a thiol scavenger, viz. N-ethyl maleimide, on intracellular thiol concentrations was also quantified. This method is useful for elucidating the role of intracellular sulfur metabolism.     

Electrochemical Synthesis of Thienoacene Derivatives: Transition-Metal-Free Dehydrogenative C−S Coupling Promoted by a Halogen Mediator

The first electrochemical dehydrogenative C−S bond formation leading to thienoacene derivatives is described. Several thienoacene derivatives were synthesized by dehydrogenative C−H/S−H coupling. The addition of ⁿBu₄NBr, which catalytically promoted the reaction as a halogen mediator, was essential.     

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.     

Analysis of Individual High-Frequency Traders’ Buy–Sell Order Strategy Based on Multivariate Hawkes Process

Traders who instantly react to changes in the financial market and place orders in milliseconds are called high-frequency traders (HFTs). HFTs have recently become more prevalent and attracting attention in the study of market microstructures. In this study, we used data to track the order history of individual HFTs in the USD/JPY forex market to reveal how individual HFTs interact with the order book and what strategies they use to place their limit orders. Specifically, we introduced an 8-dimensional multivariate Hawkes process that included the excitations due to the occurrence of limit orders, cancel orders, and executions in the order book change, and performed maximum likelihood estimations of the limit order processes for 134 HFTs. As a result, we found that the limit order generation processes of 104 of the 134 HFTs were modeled by a multivariate Hawkes process. In this analysis of the EBS market, the HFTs whose strategies were modeled by the Hawkes process were categorized into three groups according to their excitation mechanisms: (1) those excited by executions; (2) those that were excited by the occurrences or cancellations of limit orders; and (3) those that were excited by their own orders.     

New fabrication approach to develop a high birefringence photo-crosslinked film based on a sulfur-containing liquid crystalline molecule with large temperature dependence of birefringence

ABSTRACT

We present a new fabrication approach to achieve a high birefringence film by means of photopolymerization based on an alkylthio-containing rod-like liquid crystalline molecule exhibiting large temperature dependence of birefringence. We designed a new reactive mesogen having alkylthio linkages (BPM–S). It was found that BPM–S had a larger increment of birefringence with decreasing temperature, relative to commercially available alkoxy analog LC242. This result could be thought to be due to enhanced intermolecular attractive interaction for an alkylthio mesogen implied by the proximity of laterally neighboring molecules and cybotactic nematic tendency based on wide-angle X-ray measurement. The uniaxially-aligned photo-polymerized film for BPM–S showed higher birefringence than that for LC 242.