Cationic polymerization behavior of seven-membered cyclic sulfite

Cationic ring-opening polymerization behavior of a seven-membered cyclic sulfite ( 1 ) was examined. 1 was prepared by the reaction of 1,4-butanediol with SOCl₂ in 58% yield. The cationic polymerization of 1 was carried out at 0, 25, 60, or 100°C with trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), BF₃ · OEt₂, SnCl₄, methyl p-toluenesulfonate (TsOMe), or MeI as an initiator in bulk under a nitrogen atmosphere to afford the polymer with M̄_n 1000–10,400. The order of activities of the initiators for 1 was as follows, TfOH ≅ TfOMe > SnCl₄ > BF₃ · OEt₂ > TsOMe ≅ MeI. The polymerization of 1 with TfOMe afforded a poly(sulfite) below 25°C, but afforded a polymer containing an ether unit at 60°C, which was formed by a desulfoxylation. The higher the activity of the initiator was, the more easily the desulfoxylation occurred. We expected volume expansion on polymerization because cyclic sulfites have large dipole moment values, but it turned out that 1 showed 4.34% shrinkage on polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3673–3682, 1997     

Influence of contamination layer on thickness evaluation by X-ray reflectometry

In this study, the effect of allowing for a contamination layer on a SiO₂ film/Si substrate system on thickness determination by X-ray reflectometry (XRR) was investigated. The calculated XRR profiles obtained using a calculation model that utilizes a contamination layer for analysis showed good agreement with measured profiles. Further, the obtained physical structures were promising and within acceptable limits. Where the existence of a contamination layer was ignored in the calculation process, a part of the thickness of the contamination layer was incorporated into the determined thickness of the SiO₂ layer. In that case, the evaluated thickness was proportional to the density ratio between the contaminated and SiO₂ layers. The results of investigation of the effect of X-ray energy on layer thickness determination indicated that the effects of contamination also depend on the X-ray energy used for XRR measurements. These effects increase in the case of experiments that employ X-ray energy with a high contrast for the contamination.     

Resveratrol oligomers and their O-glucosides from Cotylelobium lanceolatum

Three new resveratrol oligomers, cotylelophenol C (1) (resveratrol tetramer) and cotylelosides A (2) and B (3) (O-glucosides of resveratrol trimer), together with four known glucosides of resveratrol oligomers (vaticasides A, B, C, D) and piceid, were isolated from an acetone soluble part of stem of Cotylelobium lanceolatum (Dipterocarpaceae). The structures of new compounds were determined by spectral data analysis. The characteristic properties observed in the NMR spectra of 1 were also discussed.     

Properties of bacterial cellulose transparent film regenerated from dimethylacetamide–LiCl solution

Excellent transparent films were prepared from bacterial cellulose (BC) sheets by solubilization of its defibrillated freeze‐dried specimens in a solvent of dimethylacetamide (DMAc) containing 8.0% (w/w) lithium chloride (LiCl), and their properties were compared with those of the native BC. Fibrillar structure of the native BC disappeared after dissolution, and the film formed after dissolution also loose this structure. Occurence of structural transformation from crystalline to amorphous state was also evidenced by X‐ray diffraction, solid state cross polarization/magic angle spinning ¹³C‐NMR and attenuated total reflectance–Fourier transform infrared spectroscopic analyses. In addition, excellent 3D uniform structure of the transparent BC film was further evidenced by X‐ray micro computed tomography. Plastic‐like characteristic was enhanced by film formation after dissolving the BC specimens in the DMAc–LiCl solution as shown by changing mechanical properties, a slight decrease in tensile strength (67.2 to 59.6 MPa) and breaking stress (67.2 to 58.4 MPa) but significant increase in elongation at break from 3.4 to 10.5%, and improvement of work of fracture from 5.8 to 21.2 kJ/m². Copyright © 2016 John Wiley & Sons, Ltd.     

Simultaneous enantiomeric determination of MDMA and its phase I and phase II metabolites in urine by liquid chromatography–tandem mass spectrometry with chiral derivatization

A liquid chromatography–electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) procedure was developed for the simultaneous determination of enantiomers of the prevalent designer drug 3,4-methylenedioxymethamphetamine (MDMA) and its phase I and phase II metabolites in urine with chiral derivatization. The analytes in urine were directly derivatized with chiral Marfey’s reagent, N ^α- (5-fluoro-2,4-dinitrophenyl)-d-leucinamide, without extraction. The diastereomers of the N ^α-(2,4-dinitrophenyl)-d-leucinamide derivatives generated were determined by LC-MS/MS. Satisfactory chromatographic separation was achieved for the enantiomers of MDMA and its metabolites 3,4-methylenedioxyamphetamine, 4-hydroxy-3-methoxymethamphetamine (HMMA), HMMA glucuronide, and HMMA sulfate on a semimicro octadecylsilane column using linear gradient elution. With use of multiple reaction monitoring mode, the limits of detection of these analytes ranged from 0.01 to 0.03?μg/mL. Linear calibration curves were obtained for all enantiomers from 0.1 to 20?μg/mL in urine. The method showed sufficient reproducibility and quantitative ability. This is the first report of a simple LC-MS/MS-based analytical procedure with direct chiral derivatization in aqueous media that allows simultaneous enantiomeric determination of drugs and their metabolites, including glucuronide and sulfate derivatives.     

Cu NMR/NQR Studies on Magnetism in Impurity/Hole-Doped Spin-Ladder Compounds

Cu nuclear magnetic resonance (NMR) spectra of impurities (Zn, Ni, and La)-doped spin-1/2 Heisenberg ladder compounds SrCu₂O₃ (Sr123) are broadened with Curie-like temperature (T) dependence. The spectra have been successfully fit by using a quasi-one-dimensional (Q1D) staggered polarization (SP) model. Such a SP has also revealed in Cu NMR measurements of Sr_14–x Ca _x Cu₂₄O₄₁ (Cax) with hole-doped ladders. The origin of possible 3D antiferromagnetic (AF) long-range ordering in (Zn and Ni)-doped Sr123 and Cax around x=12 at low T is considered to be similar. Once unpaired spins S ₀'s are induced and 3D interlayer interaction occurs, the localized spins couple in the whole system.     

The Erd?s-Pósa property for vertex- and edge-disjoint odd cycles in graphs on orientable surfaces

We prove that for any orientable surface S and any non-negative integer k, there exists an integer f_S(k) such that every graph G embeddable in S has either k vertex-disjoint odd cycles or a vertex set A of cardinality at most f_S(k) such that G-A is bipartite. Such a property is called the Erd?s-Pósa property for odd cycles. We also show its edge version. As Reed [Mangoes and blueberries, Combinatorica 19 (1999) 267-296] pointed out, the Erd?s-Pósa property for odd cycles do not hold for all non-orientable surfaces.