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).     

The effect of specific surface area of TiO<Subscript>2</Subscript> on the thermal decomposition of ammonium perchlorate

The thermal decomposition of ammonium perchlorate (AP) is considered to be the first step in the combustion of AP-based composite propellants. In this report, the effect of the specific surface area of titanium oxide (TiO₂) catalysts on the thermal decomposition characteristics of AP was examined with a series of thermal analysis experiments. It was clear that the thermal decomposition temperature of AP decreased when the specific surface area of TiO₂ increased. It was also possible that TiO₂ influences the frequency factor of AP decomposition because there was no observable effect on the activation energy.     

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.     

Analysis of the pure-rotational spectrum in the ν28 = 1 excited torsional state and torsional couplings of trans-ethyl methyl ether

The trans-ethyl methyl ether molecule has three low-lying torsional modes, that is, two inequivalent methyl internal rotations and an asymmetric skeletal torsion. The internal rotations of the CCH₃ and OCH₃ methyl rotors and the skeletal torsion correspond to the vibrational modes, ν₂₈, ν₂₉ and ν₃₀ respectively. In this study, the microwave absorption spectrum in the ν₂₈ = 1 CCH₃ torsional state was analyzed for the first time. Nine hundred fifty seven lines up to J = 48 and K = 4 were assigned, and the rotational, centrifugal distortion and internal rotational tunneling parameters were determined with the use of a tunneling matrix formalism. By combining the present results on the ν₂₈ = 1 torsional state with those for the ν₃₀ = 1 skeletal torsional state and the ν₂₉ = 1 OCH₃ torsional state, torsional couplings are estimated in order to understand quantitatively the inverted A/E sequence patterns observed for those three excited torsional states.     

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.     

Synthesis and properties of high‐molecular‐weight stereo di‐block polylactides with nonequivalent D/L ratios

Di‐stereoblock polylactides (di‐sb‐PLA: PLLA‐b‐PDLA) having high molecular weight (M_n > 100 kDa) were successfully synthesized by two‐step ring‐opening polymerization (ROP) of L ‐ and D ‐lactides using tin(2‐ethylhexanoate) as a catalyst. By optimizing the polymerization conditions, the block sequences were well regulated at non‐equivalent feed ratios of PLLA and PDLA. This synthetic method consisted of three stages: (1) polymerization of either L ‐ or D ‐lactide to obtain a PLLA or PDLA prepolymer with a molecular weight less than 50 kDa, (2) purification of the obtained prepolymer to remove residual lactide, and (3) polymerization of the enantiomeric lactide in the presence of the purified prepolymer. Their ¹³C and ³¹P NMR spectra of the resultant di‐sb‐PLAs strongly supported their di‐stereo block structure. These di‐sb‐PLAs, having weight‐average molecular weights higher than 150 kDa, were fabricated into polymer films by solution casting and showed exclusive stereocomplexation. The thermomechanical analysis of the films revealed that their heat deformation temperature was limited probably because of their low crystallinity owing to the non‐equivalent PLLA/PDLA ratio. The blend systems of the di‐sb‐PLAs having complementary stereo‐sequences (the one with a long PLLA block and the other with long PDLA block) were also prepared and characterized to enhance the sc crystallinity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 794–801, 2010