Lipase‐Supported Metal–Organic Framework Bioreactor Catalyzes Warfarin Synthesis

A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.     

Asymmetric Total Synthesis of ent‐Pyripyropene A

An asymmetric total synthesis of ent‐pyripyropene A was achieved by a convergent synthetic route. We used our originally developed Ti^III‐catalyzed radical cyclization to construct an AB‐ring portion that consisted of a trans‐decalin skeleton with five contiguous stereogenic centers. The coupling between the AB‐ring and the DE‐ring portions, and a subsequent C‐ring cyclization, led to the total synthesis of ent‐pyripyropene A. An evaluation of the insecticidal activity of ent‐pyripyropene A against two aphid species revealed that ent‐pyripyropene A was 35–175 times less active than naturally occurring pyripyropene A. This result indicated that the biological target of pyripyropene A recognizes the absolute configuration of pyripyropene A.     

Profiling of organosulphur compounds using HPLC-PDA and GC/MS system and antioxidant activities in hooker chive (Allium hookeri)

This study investigates the comprehensive organosulphur compounds and evaluation of antioxidant activities in Allium hookeri, called hooker chive. The non-volatile and volatile organosulphur compounds were determined by high-performance liquid chromatography-photodiode array detector (HPLC-PDA) and gas chromatography-mass spectrometry (GC-MS), respectively. Among 11 non-volatileorganosulphur compounds, methiin and cycloalliin were major compounds. A total of 42 volatile compounds were identified and allyl methyl sulphides and dimethyl sulphides were primarily volatiles. The total phenols ranged from 19.32 to 71.19 mg gallic acid equivalents (GAE)/g. The antioxidant capacities expressed IC₅₀ values ranged from 9.59 to 38.54 mg/mL for DPPH radical scavenging activity and from 0.39 to 2.36 for ferric reducing antioxidant power assay. The results were proposed as useful tools for evaluating the nutraceutical of hooker chive.     

Phosgene-free decomposition of dimethylhexane-1,6-dicarbamate over ZnO

In catalytic decomposition of dimethylhexane-1,6-dicarbamate (HDC) into hexamethylene-1,6-diisocyanate (HDI), Zn-containing homogeneous (i.e., zinc acetate) and heterogeneous (i.e., ZnO) catalysts were active among a number of catalysts tested, due to the great electron withdrawing ability of Zn ions. Particularly, when polyethylene glycol dimethyl ether was used as a solvent, ZnO was found to be relatively robust, because the catalytic performance was maintained up to the third use (HDC conversion of 93 % and HDI yield of 67 % at 180 °C for 1 h). Through investigation of a HDC/ZnO mixture at elevated temperatures by IR spectroscopy, a possible reaction scheme of ZnO-catalyzed decomposition of HDC was proposed. The H atom is removed from the N–H group of HDC by hydrogen bonding with an O site on the ZnO surface, followed by coordination of an O–C=O group in monodentate mode to a Zn site. The C–O group in the O–C=O linkage is then cleaved yielding the isocyanate and surface methoxide species. Finally, methanol is released from ZnO by a reaction between the surface methoxide and the hydroxyl species.     

Self‐Assembled Fibers Containing Stable Organic Radical Moieties: Alignment and Magnetic Properties in Liquid Crystals

Macroscopically oriented stable organic radicals have been obtained by using a liquid–crystalline (LC) gel composed of an l ‐isoleucine‐based low molecular weight gelator containing a 2,2,6,6‐tetramethylpiperidine 1‐oxyl moiety. The LC gel has allowed magnetic measurements of the oriented organic radical. The gelator has formed fibrous aggregates in liquid crystals via intermolecular hydrogen bonds. The fibrous aggregates of the radical gelator are formed and oriented on cooling by applying a magnetic field to the mixture of liquid crystals and the gelator. Superconducting quantum interference device (SQUID) measurements have revealed that both oriented and nonoriented fibrous aggregates exhibited antiferromagnetic interactions, in which super‐exchange interaction constant J is estimated as ?0.89 cm^?1.     

Preparation and characterization of a poly(vinylbenzyl sulfonic acid)‐grafted FEP membrane

In this study, a novel polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)‐grafted poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP‐g‐PVBSA), has been successfully prepared by simultaneous irradiation grafting of vinylbenzyl chloride (VBC) monomer onto a FEP film and taking subsequent chemical modification steps to modify the benzyl chloride moiety to the benzyl sulfonic acid moiety. The chemical reactions for the sulfonation were carried out via the formation of thiouronium salt with thiourea, base‐catalyzed hydrolysis for the formation of thiol, and oxidation with hydrogen peroxide. Each chemical conversion process was confirmed by FTIR, elemental analysis, and SEM‐EDX. A chemical stability study performed with Fenton's reagent (3% H₂O₂ solution containing 4 ppm of Fe²⁺) at 70 °C revealed that FEP‐g‐PVBSA has a higher chemical stability than the poly(styrene sulfonic acid)‐grafted membranes (FEP‐g‐PSSA). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 563–569, 2010     

A racemization test in peptide synthesis using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM)

Racemization of the C-terminal amino acid (Ala) has been studied in various solvents during coupling between 4-methoxybenzyloxycarbonyl (Z(OMe))-Gly-L-Ala-OH and phenylalanine benzyl ester (H-Phe-OBzl) with 4-(4,6-dimethoxy-1,3,5-thiazin-2-yl)-4-methylmorpholinium chloride (DMT-MM). The reaction occurred without substantial racemization in AcOEt, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), CH3CN, and 2-PrOH, while a slight racemization was observed in dimethyl sulfoxide (DMSO), EtOH, and MeOH. The extent of racemization may correlate with the polarity of the solvents.     

Nanoconfined heliconical structure of twist-bend nematic liquid crystal phase

We produced controlled heliconical structures of a twist-bend nematic (N_TB) liquid-crystal (LC) phase in nanoconfinement in a porous anodic aluminium oxide (AAO) film. The structural parameters of the N_TB phase such as conical angle and helical pitch can be modulated by varying the surface energy of the inner surface of the porous AAO film, done by using different self-assembled monolayers (SAMs). The LC molecules tend to be more freely packed, thus forming a larger conical angle, when placed on the tri-deca-fluoro-1,1,2,2-tetrahydrooctyl-trichlorosilane (FOTS)-treated substrate, which has a relatively low surface energy. In contrast, the molecules form a more tightly packed structure, and thus a smaller conical angle, when placed on the 2-(methoxy(polyethyleneoxy)-propyl)trimethoxysilane (PEG 6/9)-treated substrate, which has higher surface energy. This work improves our collective understanding of self-assembled heliconical structures in the N_TB phase.