Guest-to-host transmission of structural changes for stimuli-responsive adsorption property

We show that structural changes of a guest molecule can trigger structural transformations of a crystalline host framework. Azobenzene was introduced into a flexible porous coordination polymer (PCP), and cis/trans isomerizations of the guest azobenzene by light or heat successfully induced structural transformations of the host PCP in a reversible fashion. This guest-to-host structural transmission resulted in drastic changes in the gas adsorption property of the host-guest composite, displaying a new strategy for creating stimuli-responsive porous materials.     

Growth of single-crystal Ca10(Pt4As8)(Fe(1.8)Pt(0.2)As2)5 nanowhiskers with superconductivity up to 33 K

Single-crystal Ca(10)(Pt(4)As(8))(Fe(1.8)Pt(0.2)As(2))(5) superconducting (SC) nanowhiskers with widths down to hundreds of nanometers were successfully grown in a Ta capsule in an evacuated quartz tube by a flux method. Magnetic and electrical properties measurements demonstrate that the whiskers have excellent crystallinity with critical temperature of up to 33 K, upper critical field of 52.8 T, and critical current density of J(c) of 6.0 × 10(5) A/cm(2) (at 26 K). Since cuprate high-T(c) SC whiskers are fragile ceramics, the present intermetallic SC whiskers with high T(c) have better opportunities for device applications. Moreover, although the growth mechanism is not understood well, the technique can be potentially useful for growth of other whiskers containing toxic elements.     

Reactivity of a trivalent phosphorus radical cation as an electrophile toward pyridine derivatives

The reaction of methylviologen (MV²⁺) with tributylphosphine ( 1p ) and diethylphenylphosphine ( 1q ) in the presence of an alkyl-substituted pyridine ( 2 ) was found to take place through a single-electron transfer (SET) from 1 to MV²⁺ followed by nucleophilic attack by 2 on the resulting phosphine radical cation 1 ^•+. Kinetic examination showed that, in the transition state for the reaction of 1 ^•+ with 2 , an unpaired electron is largely delocalized to the pyridine moiety. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:152–157, 2000     

Polymerization of Vinyl Monomers Using Oxidase Catalysts

Polymerization of vinyl monomers using oxidase as catalyst has been performed under argon in the presence of acetylacetone as a mediator and without the use of hydrogen peroxide. The polymerization of acrylamide was catalyzed by a laccase or sarcosine oxidase catalyst in distilled water and efficiently produced the polymer with high molecular weight. In the polymerization using the laccase catalyst, the effects of temperature, time, and amounts of enzyme and mediator have been systematically investigated. On the other hand, various other oxidases such as bilirubin, choline, and xanthine oxidases showed no or little activity for the vinyl polymerization. The laccase/acetylacetone catalyst induced the polymerization of methyl methacrylate and styrene in a mixture of water and tetrahydrofuran. Laccase alone also acted as a catalyst for the vinyl polymerization of acrylamide and methyl methacrylate without acetylacetone. In the polymerization of methyl methacrylate using lipoxidase as the catalyst in the presence of acetylacetone, the reaction occurred in air.     

The radical-chain addition of aldehydes to alkenes by the use of N-hydroxyphthalimide (NHPI) as a polarity-reversal catalyst

Hydroacylation of simple alkenes with aldehydes via a radical process was successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a polarity-reversal catalyst. Thus, 5-tridecanone was obtained by the reaction of oct-1-ene with pentanal in the presence of small amounts of NHPI and dibenzoyl peroxide (BPO).     

Organic-inorganic hybrids from renewable plant oils and clay

This study deals with the preparation and properties of a new class of organic-inorganic hybrids from renewable resources. The hybrids were synthesized by an acid-catalyzed curing of epoxidized triglycerides in the presence of an organophilic montmorillonite (a modified clay). The mechanical properties were improved by the incorporation of clay in the oil-based polymer matrix. The reinforcement effect due to the addition of clay was confirmed by dynamic viscoelasticity analysis. The hybrids showed relatively high thermal stability. The co-curing of epoxidized soybean and linseed oils in the presence of clay produced hybrids with controlled mechanical and coating properties. The barrier property of the hybrid towards water vapor was superior to that of the oil polymer. The development of the present hybrids consisting of inexpensive renewable resources, triglyceride and clay is expected to contribute to global sustainability.     

Concise syntheses of immunostimulating glycolipids, α-galactosyl ceramides

α-Galactosylceramides (α-GalCers) are well known as immunostimulating agents having therapeutic potential. To facilitate the synthesis of α-GalCers and their derivatives, a novel and convergent strategy was designed, which is expected to be versatile for the preparation of a variety of analogues in a diversity-oriented fashion. As an initial demonstration of our strategy, KRN7000 and OCH were synthesized in eight steps from a common intermediate, which is easily obtainable in a multi-gram scale.     

Studies in organic mass spectrometry—II

The mass spectra of various N-aryliminopyridinium and isoquinolinium betaines have been recorded. The most prominent fragmentation process of these compounds is N-N bond cleavage with the charge retention on both the pyridine and aryl fragments. An ortho-effect has been observed in the mass spectrum of N-o-nitrophenyliminopyridinium betaine (IXa).     

Substitution reactions in the secondary ion mass spectrometry of N-methylpyridinium halides

Secondary ion mass spectra of N-methylpyridinium halides (C⁺X^?, where C⁺ is a pyridinium cation and X^? is a halogen anion) exhibit the C⁺ ions, a series of cluster ions ((C⁺)_n(X^?)_n–1) and, furthermore, remarkable [CX – R]⁺ ions (R = H or Me). The mechanism of the formation of [CX – R]⁺ ions was investigated by the use of deuterated compounds and B/E and B²/E constant linked-scan measurements. A possible explanation is proposed in which the ions are produced through substitution reactions between species constituting the C₂X⁺ cluster ions in the gas phase.