Asymmetric conjugate addition of 5-benzylfurfurals to nitroalkenes using a diaminomethylenemalononitrile organocatalyst

A pyrrolidine–diaminomethylenemalononitrile organocatalyst efficiently promotes the asymmetric direct bisvinylogous Michael addition of 5-benzylfurfural derivatives to nitroalkenes, affording the corresponding ε-regioselective addition products in high yields with up to 86% ee.     

Characterization of Alumina Gel Catalysts by Emanation Thermal Analysis (ETA)

Alumina gels made from the metal alkoxide is known to have high catalyst activity for the selective reduction of NO _x by hydrocarbons. It is also reported that the fine structure of the gels effects the activity. In this study, the effect of the preparation method on the fine structure and catalyst activity of the gels was investigated. Monolithic gels were obtained by hydrolysis of Al(sec-C₄H₉O)₃. The wet gels were dried at 90°C (xerogels), supercritically dried (aerogels), or dried after immersion in an ethanol solution of methyltrimethoxysilane (modified xerogels). The changes in the microstructure during heating were discussed using the results of TG-DTA, ETA and N₂ adsorption. The ETA curves show the ²²⁰Rn-release rate, E, of the samples, previously labelled with ²²⁸Th and ²²⁴Ra, during heating. The decrease in E of the xerogel at temperatures higher than 400°C indicates a gradual decrease in the surface area and porosity. A remarkable decrease in the BET surface area of the xerogel was found after heat-treating at 500°C. On the other hand, constant E of the aerogels and modified xerogels above 450°C suggests high thermal stability. The pore radii, estimated by BJH method, and the catalyst activities at 500°C of the aerogels and the modified xerogels were higher than those of the xerogels. The temperature range in which the alumina gels are applicable as catalysts was determined.     

Facile aerobic photo-oxidative synthesis of α-diketones from alkynes

We report a useful method for facile aerobic photo-oxidative synthesis of α-diketones from alkynes with MgBr₂·OEt₂. This procedure provides a practical synthetic method of α-diketones using easily handled bromine sources, harmless visible light, and molecular oxygen as terminal oxidant.     

HPLC enantioseparation of α,α‐diphenyl‐2‐pyrrolidinemethanol and methylphenidate using a chiral fluorescent derivatization reagent and its application to the analysis of rat plasma

Enantioseparation of α,α‐diphenyl‐2‐pyrrolidinemethanol (D2PM) and methylphenidate (MPH; Ritalin^®) using (R)‐(?)‐4‐(N,N‐dimethylaminosulfonyl)‐7‐(3‐isothiocyanatopyrrolidin‐1‐yl)‐2,1,3‐benzoxadiazole as the chiral derivatization reagent has been achieved for the first time, and a simple, reliable detection method using HPLC with fluorescence detection has been developed. D2PM and MPH have been derivatized with (R)‐(?)‐4‐(N,N‐dimethylaminosulfonyl)‐7‐(3‐isothiocyanatopyrrolidin‐1‐yl)‐2,1,3‐benzoxadiazole at 55°C for 15 min. The derivatives of D2PM and MPH have been separated, completely and rapidly, using a reversed‐phase system within 16 min (resolution factor (R_s)=1.60 and 2.53, respectively). The detection limits of (R)‐ and (S)‐D2PM were found to be 6.8 and 13 ng/mL, respectively, and those of D ‐ and L ‐threo‐MPH were 61 and 66 ng/mL, respectively (S/N=3). The proposed method was successfully applied to the analysis of rat plasma, where the rats were separately dosed with D2PM and MPH (Ritalin).     

Screening DNA Adducts by LC–ESI–MS–MS: Application to Screening New Adducts Formed from Acrylamide

A method for screening DNA adducts with unknown chemical structures was developed; it involves the use of liquid chromatography–electrospray ionization-tandem mass spectrometry (LC–ESI–MS–MS). In electrospray ionization (ESI) product ion mass spectra of guanine adducts, fragment ions were observed at m/z 152 and 135. Precursor ion scan analysis of these fragment ions indicated that the screening of DNA adducts would be possible. The developed method was used for the analysis of DNA adducts derived from acrylamide, which is not only a constituent of many commonly consumed foods but also a carcinogenic compound. We successfully discovered new guanine adducts. The results of this study indicate that the developed method is useful for screening new DNA adducts.     

Ion‐Pairing Assemblies Based on Pentacyano‐Substituted Cyclopentadienide as a π‐Electronic Anion

Pentacyanocyclopentadienide (PCCp^?), a stable π‐electronic anion, provided various ion‐pairing assemblies in combination with various cations. PCCp^?‐based assemblies exist as single crystals and mesophases owing to interionic interactions with π‐electronic and aliphatic cations with a variety of geometries, substituents, and electronic structures. Single‐crystal X‐ray analysis revealed that PCCp^? formed cation‐dependent arrangements with contributions from charge‐by‐charge and charge‐segregated assembly modes for ion pairs with π‐electronic and aliphatic cations, respectively. Furthermore, some aliphatic cations gave dimension‐controlled organized structures with PCCp^?, as observed in the mesophases, for which synchrotron XRD analysis suggested the formation of charge‐segregated modes. Noncontact evaluation of conductivity for (C₁₂H₂₅)₃MeN⁺ ? PCCp^? films revealed potential hole‐transporting properties, yielding a local‐scale hole mobility of 0.4 cm² V^?1 s^?1 at semiconductor–insulator interfaces.     

Carboxylate‐Driven Supramolecular Assemblies of Protonated meso‐Aryl‐Substituted Dipyrrolylpyrazoles

Dipyrrolylpyrazole (dpp) derivatives possessing an aryl ring at the pyrazole 4‐position were synthesized. Upon protonation, modified dpp derivatives formed a variety of assembled structures through complexation with carboxylates, as observed by single‐crystal X‐ray and synchrotron XRD analyses. In particular, the complexation of protonated dpp species possessing long alkyl chains with dicarboxylates resulted in highly ordered assembled structures, the packing modes of which as lamellar structures were controlled by the lengths of the spacer units between two carboxylate moieties. The charge‐carrier transporting properties of the solid materials were also controlled by bound anions, including dicarboxylates.     

Solid-phase extraction with C30 bonded silica for analysis of polycyclic aromatic hydrocarbons in airborne particulate matters by gas chromatography-mass spectrometry

A solid-phase extraction (SPE) method using triacontyl bonded silica (C30) as sorbent was developed for the determination of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (PAHs) in airborne particulate matters quantitatively by gas chromatography-mass spectrometry (GC-MS). Optimization experiments were conducted using spiked standard aqueous solution of PAHs and real airborne particulates samples aiming to obtain highest SPE recoveries and extraction efficiency. Factors were studied in SPE procedures including the concentration of organic modifier, flow rate of sample loading and elution solvents. The ultrasonication time and solvents were also investigated. Recoveries were in the range of 68-107% for standard PAHs aqueous solution and 61-116% for real spiked sample. Limits of detection (LODs) and limits of quantification (LOQs) with standard solution were in the range of 0.0070-0.21 microgL(-1) and 0.022-0.67 microgL(-1), respectively. The optimized method was successfully applied to the determination of 16 PAHs in real airborne particulate matters.