X-ray diffraction study on the thermal expansion behavior of cellulose Iβ and its high-temperature phase

Oriented films of cellulose prepared from algal cellulose were hydrothermally treated to convert them into highly crystalline cellulose Iβ. The lateral thermal expansion behavior of the prepared cellulose Iβ films was investigated using X-ray diffraction at temperatures from 20 to 300 °C. Cellulose Iβ was transformed into the high-temperature phase when the temperature was above 230 °C, allowing the lateral thermal expansion coefficient of cellulose Iβ and its high-temperature phase to be measured. For cellulose Iβ, the thermal expansion coefficients (TECs) of the a- and b-axes were α_a = 9.8 × 10⁻⁵ °C⁻¹ and α_b = 1.2 × 10⁻⁵ °C⁻¹, respectively. This anisotropic thermal expansion behavior in the lateral direction is ascribed to the crystal structure and to the hydrogen-bonding system of cellulose Iβ. For the high-temperature phase, the anisotropy was more conspicuous, and the TECs of the a- and b-axes were α_a = 19.8 × 10⁻⁵ °C⁻¹ and α_b = −1.6 × 10⁻⁵ °C⁻¹, respectively. Synchrotron X-ray fiber diffraction diagrams of the high-temperature phase were also recorded at 250 °C. The cellulose high-temperature phase is composed of a two-chain monoclinic unit cell, a = 0.819 nm, b = 0.818 nm, c (fiber repeat) = 1.037 nm, and γ = 96.4°, with space group = P2₁. The volume of this cell is 4.6% larger than that of cellulose Iβ at 30 °C.     

Catalytic enantioselective 1,3-dipolar cycloadditions of nitrones with propioloylpyrazoles and acryloylpyrazoles induced by chiral π-cation catalysts

A chiral copper(II) complex of 3-(2-naphthyl)-l-alanine amide successfully catalyzes the enantioselective 1,3-dipolar cycloaddition reaction of nitrones with propioloylpyrazole and acryloylpyrazole derivatives. The asymmetric environment created by intramolecular π-cation interaction gives the corresponding adducts in high yields with excellent enantioselectivity. This is the first successful method for the catalytic enantioselective 1,3-dipolar cycloaddition of nitrones with acetylene derivatives. The 1,3-dipolar cycloadducts can be stereoselectively converted to β-lactams via reductive cleavage of the N-O bond using SmI(2).     

Dynamical properties of ethylene glycol and glucose studied by temperature-modulated differential scanning calorimetry and Brillouin scattering

The fragility of ethylene glycol and glucose aqueous solution systems has been investigated by temperature-modulated differential scanning calorimetry (TMDSC). The frequency and temperature dependences of complex specific heat have been observed in the vicinity of a glass-transition temperature T _g . It is shown that the value of the fragility index m can be determined from the temperature dependence of the α-relaxation times observed by TMDSC. We have also studied the elastic properties of these aqueous solutions by micro-Brillouin scattering, and determined these relaxation times of elastic properties in the gigahertz range.     

Intermolecular π‐stacking and F...F interactions of fluorine‐substituted meso‐alkynylporphyrin

Two C2‐symmetric meso‐alkynylporphyrins, namely 5,15‐bis[(4‐butyl‐2,3,5,6‐tetrafluorophenyl)ethynyl]‐10,20‐dipropylporphyrin, C₅₀H₄₂F₈N₄, (I), and 5,15‐bis[(4‐butylphenyl)ethynyl]‐10,20‐dipropylporphyrin, C₅₀H₅₀N₄, (II), show remarkable π–π stacking that forms columns of porphyrin centers. The tetrafluorophenylene moieties in (I) show intermolecular interactions with each other through the F atoms, forming one‐dimensional ribbons. No significant π–π interactions are observed in the plane of the phenylene and tetrafluorophenylene moieties in either (I) or (II). The molecules of both compounds lie about inversion centers.     

Fully and partially fluorinated flavone derivatives

In the crystal structures of the fully and partially fluorinated flavone derivatives 5,6,7,8‐tetrafluoro‐2‐(2,3,4,5,6‐pentafluorophenyl)‐4H‐1‐benzopyran‐4‐one, C₁₅HF₉O₂, (I), and 5,6,7,8‐tetrafluoro‐2‐phenyl‐4H‐1‐benzopyran‐4‐one, C₁₅H₆F₄O₂, (II), the pentafluorophenyl group and the pyranone moiety in (I) are twisted due to repulsion of the F substituents, and a CO(δ⁻)...π(δ⁺) intermolecular interaction is observed between the carbonyl O atom and the pentafluorophenyl group. In (II), on the other hand, the phenyl group and the pyranone moiety are almost coplanar, and arene–perfluoroarene interactions are observed in the head‐to‐tail intermolecular columnar stacking between the phenyl group and the tetrafluorophenylene moiety.     

Effects of hyperons in binary neutron star mergers

Numerical simulations for the merger of binary neutron stars are performed in full general relativity incorporating both nucleonic and hyperonic finite-temperature equations of state (EOS) and neutrino cooling. It is found that even for the hyperonic EOS, a hypermassive neutron star is first formed after the merger for the typical total mass ≈2.7M(⊙), and subsequently collapses to a black hole (BH). It is shown that hyperons play a substantial role in the postmerger dynamics, torus formation around the BH, and emission of gravitational waves (GWs). In particular, the existence of hyperons is imprinted in GWs. Therefore, GW observations will provide a potential opportunity to explore the composition of neutron star matter.     

Optical pulsation mechanism based on optical near-field interactions

We theoretically demonstrate optical pulsation based on optical near-field interactions between quantum nanostructures. It is composed of two quantum dot systems, each of which consists of a combination of smaller and larger quantum dots, so that optical excitation transfer occurs. With an architecture in which the two systems take the role of a timing delay and frequency up-conversion, we observe pulsation in populations pumped by continuous-wave light irradiation. The pulsation is induced with suitable setting of parameters associated with the optical near-field interactions. This will provide critical insights toward the design and implementation of experimental nanophotonic pulse generating devices.     

Spectroscopy of the hyperfine structure of antiprotonic 4He and 3He

The spin magnetic moment $\mu^{\overline{p}}_{s}$ of the antiproton can be determined by comparing the measured transition frequencies in $\overline{p}^4$ He^?+? with three-body QED calculations. A comparison between the proton and antiproton can then be used as a test of CPT invariance. The highest measurement precision of the difference between the proton and the antiproton spin magnetic moments to date is 0.3%. A new experimental value of the spin magnetic moment of the antiproton was obtained as $\mu^{\overline{p}}_{s} = -2.7862(83)\mu_{N}$ , slightly better than the previously best measurement. This agrees with $\mu^{p}_{s}$ within 0.24%. In 2009, a new measurement with antiprotonic ³He has been started. A comparison between the theoretical calculations and experimental results would lead to a stronger test of the theory and address systematic errors therein. A measurement of this state will be the first HF measurement on $\overline{p}^3$ He^?+?. We report here on the new experimental setup and the first tests.     

Ab initio molecular orbital study on three feasible mechanisms for substitution of the vinylic carbon in F2C=C(OMs)BMe3−

A substitution on 2,2-difluorovinylic carbon was investigated by using ab initio molecular orbital calculations. Three feasible mechanisms, which are the S_N1-like, the S_N2-type and the addition-elimination mechanisms, were ex- amined for a model borate, 2,2-difluoro-1-mesyloxyvinyl(trimethyl)borate. Four TSs were obtained depending on the position of Li⁺ around the vinylborate although activation energies in the gas phase are rather high (ca. 30–40 kcal mol⁻¹) in comparison with that expected from the experimental conditions. It was confirmed at the SCRF-IPCM calculations that the solvent effect reduces the acti- vation energy of one S_N2-type mechanism very much (4. l kcal mol⁻¹ at the B3LYP/6-31+G^*//RHF/6-31+G^/s* level of theory) while those for the other mechanisms do not change very much. Therefore, the S_N2-type mechanism is applicable to the substitution reaction observed for the vinylborate.     

Immobilization of RuS2 Nanoparticles Prepared in Reverse Micellar System onto Thiol-Modified Polystyrene Particles and their Photocatalytic Properties

RuS₂ nanoparticles, smaller than 3 nm in diameter, were prepared by H₂S gas injection into the AOT/isooctane reverse micellar solution containing RuCl₃ aqueous solution. The nanoparticle size was found to be independent of the W_o (water content) value of the reverse micellar system, as shown by TEM observation. The recovery and immobilization of the RuS₂ nanoparticles from reverse micelles onto thiol-modified polystyrene particles (PSt-SH) were successfully carried out, by the addition of PSt-SH into the reverse micellar solution under conditions of mild stirring. The resulting composites, PSt-RuS₂, showed photocatalytic activity for H₂ generation form aqueous solution containing 2-propanol and Na₂SO₃ as sacrificial electron donors.