Metallocene copolymers of propene and 1‐hexene: The influence of the comonomer content and thermal history on the structure and mechanical properties

The relationships between the structure and properties have been established for copolymers of propylene and 1‐hexene synthesized with an isotactic metallocene catalyst system. The most important factor affecting the structure and properties of these copolymers is the comonomer content. The thermal treatment, that is, the rate of cooling from the melt, is also important. These factors affect the thermal properties, the degree of crystallinity, and therefore the structural parameters and the viscoelastic behavior. A slow cooling from the melt favors the formation of the γ phase instead of the α modification. Regarding the viscoelastic behavior, the β relaxation, associated with the glass‐transition temperature, is shifted to lower temperatures and its intensity is increased as the 1‐hexene content raises. The microhardness values are correlated with those of the storage modulus deduced from dynamic mechanical thermal analysis curves, and good linear relations have been obtained between these parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1253–1267, 2006     

Characterization and electrical properties of polypyrrole/multiwalled carbon nanotube composites synthesized by in situ chemical oxidative polymerization

This study describes the preparation of polypyrrole (PPy)/multiwalled carbon nanotube (MWNT) composites by in situ chemical oxidative polymerization. Various ratios of MWNTs, which served as hard templates, were first dispersed in aqueous solutions with the surfactant cetyltrimethylammonium bromide to form micelle/MWNT templates and overcome the difficulty of MWNTs dispersing into insoluble solutions of pyrrole monomer, and PPy was then synthesized via in situ chemical oxidative polymerization on the surface of the templates. Raman spectroscopy, Fourier transform infrared (FTIR), field‐emission scanning electron microscopy (FESEM), and high‐resolution transmission electron microscopy (HRTEM) were used to characterize the structure and morphology of the fabricated composites. Structural analysis using FESEM and HRTEM showed that the PPy/MWNT composites were core (MWNT)–shell (PPy) tubular structures. Raman and FTIR spectra of the composites were almost identical to those of PPy, supporting the idea that MWNTs served as the core in the formation of a coaxial nanostructure for the composites. The conductivities of these PPy/MWNT composites were about 150% higher than those of PPy without MWNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1413–1418, 2006     

Novel photoswitching dithienylethenes with ferrocene units

Two novel dithienylethenes with ferrocene units were synthesized by Wittig reaction. The structure of 2a has been established by X‐ray diffraction studies. They could reversibly interconvert between two thermally stable forms, an open and a closed one, using light of different wavelengths as triggers. Copyright © 2006 John Wiley & Sons, Ltd.     

Retracted: Determination of scutellarin isomer,a predominant metabolite of scutellarin,in human plasma by HPLC/tandem mass spectrometry and its application to a pharmacokinetic study in Chinese healthy volunteers

Retraction: The following article from Biomedical Chromatography, “Determination of scutellarin isomer, a predominant metabolite of scutellarin, in human plasma by HPLC/tandem mass spectrometry and its application to the pharmacokinetic study in Chinese healthy volunteers” by Chun‐hua Xia, Yu‐qing Xiong, and Guang‐ji Wang, published online on 21 June 2007 in Wiley Interscience (www.interscience.wiley.com/journal/bmc), has been retracted at the authors' request.     

Studies on extraction of beryllium by di-(2-ethyl hexyl)-phosphoric acid from hydrochloric acid solutions

The distribution of Be between aqueous HCl solutions and organic phases of di-(2-ethyl hexyl)-phosphoric acid, has been described. The dependence of extraction on aqueous acidity, metal and extractant concentration as also on the diluent type, was thoroughly examined. The possible mechanism of extraction has been discussed in the light of results obtained.     

Immunosuppressive ent‐Kaurene Diterpenoids from Isodon serra

Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3).     

Characterization of the new Bi∼6.2Cu∼6.2O8(PO4)5 oxyphosphate; a disordered compound containing 2- and 3-O(Bi, Cu)4 tetrahedra—wide polycationic ribbons

The present work is dedicated to the XRD, ED and HREM characterization of a new bismuth copper oxyphosphate Bi_∼6.2Cu_∼6.2O₈(PO₄)₅ (a=11.599(2)Å, , c=37.541(5)Å, R₁=0.0755, Rw₂₌0.174, G.S Pn2₁a). The relatively long size of its c parameter is due to the arrangement along this direction of two kinds of ribbon-like polycations formed by edge sharing O(Bi, Cu)₄ tetrahedra. The existence of such cations is characterized by the b∼5.2 Å value intrinsic to the ribbons structure and commonly found in bismuth oxyphosphate materials. In the title compound, 2-tetrahedra wide [Bi_∼2.4Cu_∼3.6O₄]^6.4+ and 3-tetrahedra wide [Bi_∼5Cu_∼3O₆]⁹⁺ ribbons are isolated by phosphate groups and alternate along c. The interstitial site created between two different sizes ribbons is occupied by Cu²⁺ cations disordered over several close crystallographic sites. The mixed Bi³⁺/Cu²⁺ nature of certain edge-of-ribbons positions induces a disorder over several configurations of the phosphate groups. The concerned oxygen atoms form the environment of the disordered interstitial Cu²⁺ cations which occupy tunnels formed by the phosphate anions. The high-resolution electron microscope study enables a precise correlation between the observed images and the refined crystal structure, evidencing the polycations visualization. Furthermore, this material being the second example of partially disordered compound similar chemical system, some topological rules can be deduced. The b-axis doubling was observed by ED and HREM and is assigned to the ordering of interstitial Cu²⁺ within tunnels cations. A partial intra-tunnel ordering was also observed.     

Structure‐Dependent Photoinduced Electron Transfer in Fullerodendrimers with Light‐Harvesting Oligophenylenevinylene Terminals

Oligophenylenevinylene (OPV)‐terminated phenylenevinylene dendrons G1 – G4 with one, two, four, and eight “side‐arms”, respectively, were prepared and attached to C₆₀ by a 1,3‐dipolar cycloaddition of azomethine ylides generated in situ from dendritic aldehydes and N‐methylglycine. The relative electronic absorption of the OPV moiety increases progressively along the fullerodendrimer family C₆₀G1 – C₆₀G4 , reaching a 99:1 ratio for C₆₀G4 (antenna effect). UV/Vis and near‐IR luminescence and transient absorption spectroscopy was used to elucidate photoinduced energy and electron transfer in C₆₀G1 – C₆₀G4 as a function of OPV moiety size and solvent polarity (toluene, dichloromethane, benzonitrile), taking into account the fact that the free‐energy change for electron transfer is the same along the series owing to the invariability of the donor–acceptor couple. Regardless of solvent, all the fullerodendrimers exhibit ultrafast OPV→C₆₀ singlet energy transfer. In CH₂Cl₂, the OPV→C₆₀ electron transfer from the lowest fullerene singlet level (¹C₆₀*) is slightly exergonic (ΔG_CS≈0.07 eV), but is observed, to an increasing extent, only in the largest systems C₆₀G2 – C₆₀G4 with lower activation barriers for electron transfer. This effect has been related to a decrease of the reorganization energy upon enlargement of the molecular architecture. Structural factors are also at the origin of an unprecedented OPV→C₆₀ electron transfer observed for C₆₀G3 and C₆₀G4 in apolar toluene, whereas in benzonitrile, electron transfer occurs in all cases. Monitoring of the lowest fullerene triplet state by sensitized singlet oxygen luminescence and transient absorption spectroscopy shows that this level is populated through intersystem crossing and is not involved in photoinduced electron transfer.     

A zwitterion of 1,5‐bis­(2‐hydroxy­benzamido)‐3‐aza­pentane: a two‐dimensional hydrogen‐bonding network involving dimers

The title compound, 2‐{N‐[2‐(2‐hydroxy­benzamido)ethyl­ammonio­ethyl]amino­carbon­yl}phenolate, C₁₈H₂₁N₃O₄, crystallizes in a zwitterionic form as a result of inter­molecular proton transfer and possesses a negatively charged phenolate group and a protonated amino group. The 2‐hydroxy­benzamide and 2‐(amino­carbonyl)­phenolate moieties attached to the two ends of the C—C—N—C—C backbone adopt a cis conformation in relation to this backbone. All N‐ and O‐bound H atoms are involved in hydrogen‐bond formation; the zwitterions are first linked into head‐to‐tail dimers, which are further organized into a two‐dimensional network parallel to the crystallographic bc plane.     

Synthesis of 2‐Dihydrooxadiazolinyl Chromones

Reactions of the substituted 2‐formyl chromones with aroylhydrazines gave corresponding 2‐(aroylhydrazonomethylidyne) chromones. Then 2‐(3′‐acetyl‐5′‐aryl‐2′,3′‐dihydro‐1′,3′,4′‐oxadiazol‐2′‐yl) chromones were prepared by these 2‐(aroylhydrazonomethylidyne) chromones under refluxing with Ac₂O. All target compounds were characterized through elemental analysis and IR, ¹H NMR, MS.