Synthesis,optical and electrochemical properties of arylenevinylene‐based π‐conjugated polymers with imidazolium units in the main chain

Arylenevinylene‐based π‐conjugated polymers containing imidazolium cationic units in the main chain and their model compounds were synthesized and characterized in terms of optical and electrochemical properties. 9,9‐Bisoctylfluorene, 2,5‐bisdodecyloxybenzene, and 3‐dodecylthiophene were introduced as arylene units with different donor characteristics to evaluate the effect on the highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gap energy. The UV–vis and fluorescence spectra of cationic polymers and model compounds with iodide counter anion exhibited a significant blue shift with respect to the parent neutral molecules. X‐ray single crystal analysis for model compounds revealed that the effective π‐conjugation length of cationic model compounds decreased compared to the neutral model compounds by means of twisted conformation directed by CH‐π interactions between N‐methyl groups of imidazolium and neighboring aryl units. The cyclic voltammetry measurement suggested the negative shift of LUMO levels by the conversion of imidazole to imidazolium, indicating the electron‐accepting characteristics of cationic imidazolium unit. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Formal meta-specific intramolecular Friedel–Crafts allylic alkylation of phenols through a spirocyclization–dienone–phenol rearrangement cascade

Formal meta-specific intramolecular Friedel–Crafts allylic alkylation of phenols was achieved based on spirocyclization–dienone–phenol rearrangement cascades. Systematic screening of acid catalysts revealed that Sc(OTf)₃ was a highly effective catalyst for dienone–phenol rearrangement of spiro[4.5]cyclohexadienones. Using 5 mol % of Sc(OTf)₃ as the promoter, various spirocyclic substrates were transformed into the corresponding phenol derivatives in good to excellent yield. Furthermore, the one-pot sequential spirocyclization–dienone–phenol rearrangement proceeded using a palladium and scandium multi-catalytic system or a triphenylmethyl cation single-catalyst system, providing the corresponding meta-allylated phenol derivatives in excellent yield.     

Colorimetric detection of Ni2+ based on an anionic triphenylmethane dye and a cationic polyelectrolyte in aqueous solution

The combination of xylenol orange (XO) and poly(diallyldimethylammonium chloride) (PDADMAC) has been utilized as a colorimetric sensor for selective recognition of Ni²⁺ in aqueous solution. Upon addition of Ni²⁺, the chemosensor exhibited the significant color change from red to purple with a bathochromic shift, whereas these change was not induced by other metal ions. XO alone did not recognize Ni²⁺ colorimetrically, indicating that PDADMAC was required for detecting Ni²⁺. This study can provide the facile method for the construction of new chemosensors by a simple mixture of an anionic water-soluble dye and cationic polyelectrolyte.     

57Fe Mössbauer study YBa2Cu3−xFexO7−y

Mössbauer measurement is made on the system YBa₂Cu_3?xFe_xO_7?y (0.03≤x≤1.0) at various temperatures. It is found that the sites occupied by Fe ions can be classified into major two and minor one groups. The isomer shifts for the major two groups are nearly zero relative to metallic iron, and their quadrupole splittings are large (about 1.9 and 1.1 mm/s). By comparison of the spectra measured before and after a heat-treatment in vacuum, it is concluded that the Fe ions with the largest quadrupole splitting occupy the pyramidal sites, and the other the planer sites. Two different hyperfine magnetic fields (240 and 442 k0e) are observed at 1.7 K for the specimen with x=0.2. It is proposed that the valence states of Fe ions of the major two groups are pentavalent.     

Determination of cadmium and bismuth in high-purity zinc metal by inductively coupled plasma mass spectrometry with on-line matrix separation

Traces of cadmium and bismuth in high-purity zinc metal were determined by inductively coupled plasma mass spectrometry (ICP-MS) in combination with flow injection (FI) on-line matrix separation (FI-ICP-MS). The anion-exchange separation method of the potassium iodide (KI) system was applied to the separation of the analytes from the matrix zinc. The analytes, cadmium and bismuth, were adsorbed on the anion-exchange (BIO. RAD AG1-X8) mini-column (1.0 mm i.d.x 100 mm bed length), while the matrix zinc can be completely removed from the anion-exchange resin. The analytes were eluted by 2 mol/l HNO(3) and directly introduced into the ICP-MS. The detection limits (D.L.) obtained by using a single injection (350 microl) were 0.81 and 0.075 ng g(-1) for cadmium and bismuth, respectively. In the case of multi-injection concentration onto the anion-exchange mini-column (five injections 350 microl each), the detection limits could be improved to 0.16 and 0.014 ng g(-1) for cadmium and bismuth, respectively. The reproducibilities of the single injection and the multi-injection method were satisfactory with a relative standard deviation of less than 5% (at the 10 and 1 ng ml(-1) level for the single injection and the multi-injection method, respectively). The method was successfully applied to the determination of trace impurities in four samples of high-purity zinc metal (7 nines grade) and three standard reference materials of high-purity unalloyed zinc samples (from NIST).     

Fluorescence detection of ATP based on the ATP-mediated aggregation of pyrene-appended boronic acid on a polycation

A novel fluorescent sensing system for ATP has been created utilizing the ATP-mediated aggregation process of pyrene-appended boronic acid on a polycation.     

A new approach for the investigation of isoprenoid biosynthesis featuring pathway switching,deuterium hyperlabeling,and 1H NMR spectroscopy. The reaction mechanism of a novel streptomyces diterpene cyclase

Recent methodology for the investigation of isoprenoid biosynthesis featuring pathway switching and hyperdeuteration has shown significant advantages in elucidating the reaction mechanism of a novel Streptomyces diterpene cyclase with use of precise atom-level analysis. Insight into the cyclization mechanism involved in the conversion of geranylgeranyl diphosphate (GGPP) into a clerodane hydrocarbon terpentetriene was obtained by heterologous expression in doubly engineered Streptomyces lividans of a diterpene cyclase gene derived from Streptomyces griseolosporeus, a producer of an unique diterpenoid cytotoxic antibiotic terpentecin, and by in vivo labeling with mevalonate-d(9). The cyclization involved electrophilic protonation, cationic ring closure, Wagner-Meerwein-type rearrangements, and deprotonation. A key feature was that the labeled metabolite as a mixture of predominantly deuterated mosaic molecules provided sufficient information that close analysis of the labeling pattern for each individual isoprene unit was achieved primarily by (1)H NMR spectroscopy. The cyclization of GGPP into the clerodane skeleton catalyzed by the cyclase appears to involve Si-face specific protonation, intermediates with A/B chair-boat conformation, and specific methyl and hydride migrations to give an intermediary C-4 carbocation. Subsequent collapse of the cation through specific removal of the initiating proton and final elimination of diphosphate gives rise to the terpentetriene hydrocarbon.     

Three-variable reversible Gray-Scott model

Even though the field of nonequilibrium thermodynamics has been popular and its importance has been suggested by Demirel and Sandler [J. Phys. Chem. B 108, 31 (2004)], there are only a few investigations of reaction-diffusion systems from the aspect of thermodynamics. A possible reason is that model equations are complicated and difficult to analyze because the corresponding chemical reactions need to be reversible for thermodynamical calculations. Here, we introduce a simple model for calculation of entropy production rate: a three-variable reversible Gray-Scott model. The rate of entropy production in self-replicating pattern formation is calculated, and the results are compared with those reported based on the Brusselator model in the context of biological cell division.     

Clavulones,new type of prostanoids from the stolonifer clavulariaviridis quoy and gaimard

Three new prostanoids, clavulone I($\text{1}$), II($\text{2}$) and III($\text{3}$), were isolated from the Japanese Stolonifer $\text{Claularia}$$\text{viridis}$ Quoy and Gaimard. The structures of these prostanoids were determined on the basis of spectral data and chemical reactions.