Computational analysis of bending strain in single chains of β‐PVDF

Hartree–Fock calculations on 20 carbon atom chains of β‐phase poly(vinylidene fluoride) (PVDF) were done as a function of bending strain. The results can be modeled in terms of a classical energy versus strain curve resulting in a pseudomodulus (310 GPa) comparable to the Young's modulus calculated for stretching along carbon atom chain (199 GPa). The model also shows that the minimum energy state of a single chain of the polymer is not linear in the all‐trans geometry and that a significant strain energy is stored in natural thin films. This suggests that energy can be captured from bending motions in β‐PVDF. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1493–1495, 2011     

Molecular motion of polycarbonate included in γ‐cyclodextrin

Molecular motions of single polycarbonate (PC) chains threaded into crystalline γ‐cyclodextrin (γ‐CD) channels were examined using solid‐state ¹³C NMR and molecular dynamics simulations. The location of PC within the channels was confirmed by spin diffusion from a PC ¹³C label to natural‐abundance ¹³C of the γ‐CD. Rotor‐encoded longitudinal magnetization (RELM) (under 7‐kHz magic‐angle sample‐spinning conditions) was combined with multiple‐pulse ¹H‐¹H dipolar decoupling to detect large‐amplitude phenyl‐ring motion in both bulk PC and polycarbonate γ‐cyclodextrin inclusion compound (PC‐γ‐CD). The RELM results indicate that the phenyl rings in PC‐γ‐CD undergo 180° flips faster than 10 kHz just as in bulk PC. The molecular dynamics simulations show that the frequency of the phenyl‐ring flips depends on the cooperative motions of PC atoms and neighboring atoms of the γ‐CD channel. The distribution of protonated aromatic‐carbon laboratory and rotating‐frame ¹³C spin‐lattice relaxation rates for bulk PC and PC‐γ‐CD are similar but not identical. The distributions for both systems arise from site heterogeneities. For bulk PC, the heterogeneity is attributed to variations in local chain packing, and for PC‐γ‐CD the heterogeneity arises from variations in the location of the PC phenyl rings in the γ‐CD channel. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1271–1282, 2007     

Crystallization of bisphenol‐A polycarbonate by a vacuum process

The surface of bisphenol‐A‐polycarbonate (BAPC) showing a stable amorphous state can be crystallized by the “vapor transportation method”. Crystallized BAPC was employed as the novel simple storage medium and bit patterns were recorded on its surface by laser irradiation. Copyright © 2004 John Wiley & Sons, Ltd.     

Absolute Konfiguration von α-Zeacarotin, α-Apo-8-carotinal und α-Apo-8-carotinol

α-Zeacarotene, isolated from corn gluten, has been shown to have the same absolute configuration at C(6) as natural (+)-α-carotene. Chiroptical comparison was made with the derived α-apo-8-carotenole. The same chirality has been found with δ-, ε-carotene, lutein, semi-α-carotenone, zeinoxanthin, crocoxanthin and β,ε-carotene-2-ol. Therefore, biological cyclisation of the acyclic precursor to the α-ionone ring seems to be stereospecific and is probably different (enantiomeric) to that leading to β-ionone derivatives. Cotton effects of carotenoids have for the first time been measured in the visible region. All carotenoids examined with C(6)-R-chirality show a positive effect at their longest absorption band.     

A simple derivation of the exponent γ for Gaussian chains with excluded volume

The exponent γ in the expression for the partition function Z ≅ μ^N · N^γ−1 is derived for a Gaussian chain. The method of Ullman is adopted. Results of calculations show that for 1, 2, 3 and 4 dimensions, γ = 1, 1,25, 1,2 and 1, respectively. It is also shown that γ remains unity for all dimensions higher than four. These results are in better agreement with exact computer simulation results than the first-order renomalization group theory calculations. The self consistency of the present method and possible improvements along the lines of the present study are discussed.     

(—)β-Lycorane

Hydrogenation of diacetyllycorine (Ib) was found to be the most effective route for conversion of lycorine (Ia) into β-dihydrocaranine (II). The Hauptmann reduction of 1-deoxy-β-dihydrolycorin-2-one (XII) or the Clemmensen reduction of 1-0-acetyl-β-dihydrolycorinone (XI) followed by hydrogenation afforded (—)β-lycorane (X), which, in view of the sequence of reactions used in these transformations, is considered to have the same configurational structure as the skeleton of β-dihydrocaranine. This lycorane was also obtained by the Hauptmann reduction of β-dihydrocaranone (VIII). A procedure for preparing (—)-lycorane (V) from 1-0-acetyllycorin-2-one (XIV) was also worked up.     

Polyesters,polycarbonate, and polyurethanes from a novel monomer: α,α,α′,α′-tetramethyl-1,4-tetrafluorobenzenedimethanol

The novel diol monomer, α,α,α′,α′-tetramethyl-1,4-tetrafluorobenzenedimethanol, has been synthesized by a convenient route which involves the addition of acetone to 1,4-dilithiotetrafluorobenzene and can be purified by washing with hexanes. It does not directly undergo condensation polymerizations with diacid chlorides. Its disodium salt, prepared by its reaction with sodium hydride, similarly fails to undergo such polymerizations readily. However, the dilithium salt, prepared in situ by the reaction of the title diol with 2 equiv of n-butyllithium in tetrahydrofuran, is suitable for the preparation of various classes of condensation polymers. Four polyesters and one polycarbonate derived from the reactions of the dilithium salt of the diol with adipoly dichloride, sebacoyl dichloride, isophthaloyl dichloride, terephthaloyl dichloride, and phosgene and two polyurethanes derived from its reactions with tolylene-2,4-diisocyanate and methylene-di-1,4-phenyl diisocyanate were prepared. Each was fully characterized by GPC, NMR, IR, and UV-visible spectroscopies, and the results of these studies are reported herein. © 1993 John Wiley & Sons, Inc.     

A study on feasibility of insect—control with γ-ray

Insect-control with Co-γ-ray is a method for conserving archives, books, cotton textiles, historical relics, wood structured houses and furniture, which are called irradiated objects later on. The temporary and residual effects of γ-ray on irradiated objects and the biological effects on insects are presented in this report.

Our study shows that there is no obvious harmful effect on irradiated objects when the ray is below 870 Gy, while there is obvious deterioration on the objects when the ray is above 870 Gy. On the other hand, the ray below 870 Gy is strong enough for the insects. In fact, at the dose of 43.5–130.5 Gy, the irradiated insects could be damaged on reproductive function, even sterilized, or killed.