Solid‐state NMR analyses of the crystalline–noncrystalline structure and its thermal changes for ethylene ionomers

The crystalline–noncrystalline structure and its structural changes from thermal treatments for ethylene ionomers have been investigated with solid‐state ¹³C and ²³Na NMR spectroscopy. ¹³C spin–lattice relaxation time (T_1C) measurements reveal that as‐received ethylene ionomers have much enhanced molecular mobility in the crystalline region in comparison with conventional polyethylene samples. By appropriate annealing, however, polyethylene‐like morphological features reflecting T_1C behavior can also be observed. ¹³C spin–spin relaxation time (T_2C) measurements for the noncrystalline region reveal the existence of two components with different T_2C values, and these two components have been assigned to the crystalline–amorphous interfacial and rubbery–amorphous components. These results indicate that the structure of the major part of the noncrystalline region in the ethylene ionomers is similar to that of bulk‐crystallized polyethylene samples, regardless of possible ionic aggregates. The origin of the lower temperature endothermic peak in the heating process of the differential scanning calorimetry curve observed for the as‐received sample has also been examined somewhat in detail. As a result, it is proposed that the melting of smaller crystallites produced during storage at room temperature is the origin of the lower temperature peak. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1142–1153, 2002     

Proton magnetic resonance studies of the phase structure of bulk-crystallized linear polyethylene

The broad-line proton NMR spectra of melt-crystallized samples of polyethylene covering a very wide range in molecular weight have been analyzed in terms of contributions from three components: (1) a crystalline region with crystals of orthorhombic form; (2) a noncrystalline region with liquid-like character which produces a Lorentzian contribution to the spectrum; and (3) an intermediate region in which the rotation of methylene groups about C—C bonds is partly hindered. The relative mass fractions as well as the character of these components depend greatly on the molecular weight. Samples of low molecular weight (e.g., ?30,000) are predominantly composed of lamellar crystalline regions with a minor amount of interfacial regions and no liquid-like interzonal regions. As the molecular weight increases beyond 45,000, an interzonal region with a liquid-like character associated with a higher molecular mobility is produced. Above a molecular weight of 100,000, this liquid-like character becomes pronounced with an increase in molecular mobility in the interfacial region.     

Three-dimensional fermi-liquid ground state in the quasi-one-dimensional cuprate PrBa(2)Cu(4)O(8)

The interchain resistivity of PrBa(2)Cu(4)O(8) has been measured in high magnetic fields up to 30 T. Co-herent interchain transport at low temperatures is destroyed by a large magnetic field applied perpendicular to the CuO chains. Comparisons with quasiclassical transport theory provide strong experimental support for a three-dimensional Fermi-liquid ground state in PrBa(2)Cu(4)O(8), despite extreme anisotropy in its electronic properties and the presence of strong electron correlations.     

TEM study of band-like cellulose assemblies produced by Acetobacter xylinum at 4 °C

Two kinds of band-like cellulose assemblies, coarse and densestructures, are produced in Hestrin–Schramm medium at 4 °Cusing smooth colonies isolated from Acetobacter xylinumATCC23769, whereas ribbon cellulose assemblies are produced by the samecoloniesat 28 °C. The dense and the coarse band-like assembliesconsist of many strand-like cellulose entities (strands) and areextruded perpendicularly to the long axis of the bacterial cell. In an earlystage of incubation at 4 °C, the dense band-like assembly isproduced and the number of strands decreases gradually with increasingincubation time at 4 °C, probably because the number of activeTC subunits decreases as a result of the low-temperature shock for thebacteria.In contrast, the coarse band-like assembly is clearly observed after about 1h of incubation at 4 °C. The number of strands inthe coarse band-like assembly is about one third of that of the dense band-likeassembly and does not change during the incubation time of about 6h. In the selected-area electron diffraction (ED) experiment, thedense band-like assembly gives crystalline reflections corresponding to thecellulose II type crystal, while the coarse band-like assembly does not giveanycrystalline reflections under the same ED conditions.     

Straightforward synthesis of fucoxanthin short-chain derivatives via modified-Julia olefination

Fucoxanthin is an essential pigment for the light-harvesting of aquatic algae. It exhibits high energy transfer efficiencies to Chl a (>80%) as well as peridinin (>95%). In order to verify the generality and specificity of the noticeable observation on the ICT excited energy state character, which was found in the study of peridinin, we achieved the straightforward synthesis of a series of fucoxanthin short-chain derivatives via the modified-Julia olefination with the aldehyde half segment possessing a β,γ-epoxyketone function. The established method was successfully applied to the synthesis of the epoxy olefin derivative as an allene modified fucoxanthin analogue.     

Observation of D+ → K(+)η(') and search for CP violation in D+ → π(+)η(') decays

We report the first observation of the doubly Cabibbo-suppressed decays D(+)→K(+)η((')) using a 791 fb(-1) data sample collected with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. The ratio of the branching fractions of doubly Cabibbo-suppressed relative to singly Cabibbo-suppressed D(+)→π(+)η((')) decays are B(D(+)→K(+)η)/B(D(+)→π(+)η)=(3.06±0.43±0.14)% and B(D(+)→K(+)η')/B(D(+)→π(+)η')=(3.77±0.39±0.10)%. From these, we find that the relative final-state phase difference between the tree and annihilation amplitudes in D(+) decays, δ(TA), is (72±9)° or (288±9)°. We also report the most precise measurements of CP asymmetries to date: A(CP)(D(+)→π(+)η)=(+1.74±1.13±0.19)% and A(CP)(D(+)→π(+)η')=(-0.12±1.12±0.17)%.     

Fluorescence Response and Self-Assembly of a Tweezer-Type Synthetic Receptor Triggered by Complexation with Heme and Its Catabolites

There is increasing interest in the development and applications of synthetic receptors that recognize target biomolecules in aqueous media. We have developed a new tweezer-type synthetic receptor that gives a significant fluorescence response upon complexation with heme in aqueous solution at pH 7.4. The synthetic receptor consists of a tweezer-type heme recognition site and sulfo-Cy5 as a hydrophilic fluorophore. The receptor–heme complex exhibits a supramolecular amphiphilic character that facilitates the formation of self-assembled aggregates, and both the tweezer moiety and the sulfo-Cy5 moiety are important for this property. The synthetic receptor also exhibits significant fluorescence responses to biliverdin and bilirubin, but shows very weak fluorescence responses to flavin mononucleotide, folic acid, and nicotinamide adenine dinucleotide, which contain smaller π-scaffolds.