Quantitative comparison of a corona-charged aerosol detector and an evaporative light-scattering detector for the analysis of a synthetic polymer by supercritical fluid chromatography

A corona-charged aerosol detector (CAD) was developed to improve the sensitivity, reproducibility and quantitativeness of detection as compared to evaporative light-scattering detector (ELSD) for liquid chromatography. Our laboratory used the corona CAD as a detector for supercritical fluid chromatography (SFC) and evaluated its performance compared to the ELSD by using a certified reference material of poly(ethylene glycol) (PEG) and a well-defined equimass mixture of uniform PEG oligomers. The corona CAD was able to detect a 10 times more dilute solution of uniform oligomers compared to the ELSD. Although the original data of molecular mass by ELSD was 4.6% smaller than the certified value of PEG 1000, molecular mass distribution obtained by corona CAD was virtually almost the same as the certified value without any calibrations.     

Odd-even effect and metal induced structural convergence in self-assembled monolayers of bipyridine derivatives

Scanning tunneling microscopy (STM) observations reveal that bipyridine derivatives which exhibit various two-dimensional structures due to the odd-even chain length effect are converged into a lamellar structure upon metal coordination.     

Cowaniin, a C-glucosidic ellagitannin dimer linked through catechin from Cowania mexicana

A new complex tannin, cowaniin (1) was isolated from the leaves and stems of Cowania mexicana (Rosaceae), and its structure was characterized as novel C-glucosidic tannin dimer linked through (+)-catechin on the basis of spectral and chemical evidence. The inhibitory effect on activation of the Epstein-Barr virus early antigen was assessed for cowaniin. Six known polyphenols and related compounds, including a nitrile glucoside, purshianin, were also characterized.     

Sesquiterpene lactone glycosides from the roots of Ferula varia

Seven new sesquiterpene lactone glycosides (1-7) were isolated from the H2O-soluble fraction from the MeOH extract of the roots of Ferula varia. Their structures were elucidated by extensive spectroscopic analyses. The absolute configurations of compounds 1 and 2 were determined by modified Mosher's method.     

Biosynthesis of phytoecdysteroids in Ajuga hairy roots: clerosterol as a precursor of cyasterone, isocyasterone and 29-norcyasterone

Feeding studies of six ¹³C-labeled sterols, including clerosterol, to hairy roots of Ajugareptans var. atropurpurea have established that clerosterol is a precursor of three phytoecdysteroids, cyasterone, isocyasterone and 29-norcyasterone.     

Reversible PtII–CH3 deuteration without methane loss: metal–ligand cooperation vs. ligand-assisted PtII-protonation

Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)Pt^II(CH₃)₂, reacts with CD₃OD at 25 °C to undergo complete deuteration of Pt–CH₃ fragments in ∼5 h without loss of methane to form (dpk)Pt^II(CD₃)₂ in virtually quantitative yield. The deuteration can be reversed by dissolution in CH₃OH or CD₃OH. Kinetic analysis and isotope effects, together with support from density functional theory calculations indicate a metal–ligand cooperative mechanism wherein DPK enables Pt–CH₃ deuteration by allowing non-rate-limiting protonation of Pt^II by CD₃OD. In contrast, other model di(2-pyridyl) ligands enable rate-limiting protonation of Pt^II, resulting in non-rate-limiting C–H(D) reductive coupling. Owing to its electron-poor nature, following complete deuteration, DPK can be dissociated from the Pt^II-centre, furnishing [(CD₃)₂Pt^II(μ-SMe₂)]₂ as the perdeutero analogue of [(CH₃)₂Pt^II(μ-SMe₂)]₂, a commonly used Pt^II-precursor.

Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)Pt^II(CH₃)₂, reacts with CD₃OD at 25 °C to undergo complete deuteration of Pt–CH₃ fragments in ∼5 h without loss of methane to form (dpk)Pt^II(CD₃)₂ in virtually quantitative yield.     

Laser isotope separation of 13C by an elimination method

An elimination method is presented for laser isotope separation. It consists of flow cycles of feed molecules, in which an isotope component of non-interest, instead of the one of interest, is photolyzed to be eliminated, and the residue is recycled for photlysis. An isotope can be enriched as much as desired even if the isotope selectivity in the photolysis is low. The separation of ¹³C is demonstrated by employing multiphoton dissociation using a TEA CO₂ laser.     

Alternating copolymerization of propylene oxide and carbon dioxide with an alumina supported diethylzinc catalyst

Diethylzinc was allowed to react with γ-alumina in n-heptane at 50°C, and the copolymerization of propylene oxide and carbon dioxide was investigated in some detail at 30–90°C by using the reaction product as a catalyst. From an analysis of the catalyst it was found that diethylzinc reacted with the surface hydroxyl groups of γ-alumina mainly to give the following A-type species by evolving ethane: The catalyst showed considerably high activity for the copolymerization. The polymer obtained was a white solid with a high molecular weight soluble in benzene, acetone, dioxane, and methylene chloride and insoluble in diethyl ether and water. It was confirmed as an alternate copolymer of propylene oxide and carbon dioxide. The copolymerization was also conducted with a reaction mixture of the catalyst and catechol in which the molar ratio of catechol to the A-type species was varied. The copolymerization activity decreased linearly with an increase in the molar ratio and disappeared completely at the molar ratio of unity. On the basis of these results it has been concluded that the A-type is the true active species for the copolymerization.     

Organometallic polymers containing tricarbonyl(η4-diene)-ruthenium(0) and -iron(0) as pendant groups

Vinyl ethers containing tricarbonyl(14-η⁴-1,3-pentadiene)-ruthenium(0) and -iron(0) species were prepared utilizing selective dienylation with penta-dienylpotassium and were polymerized with cationic initiators to give high molecular weight polymers. The diene-metal moieties were converted into tricarbonyl(13-η³-allyl)metal species by protonation with dry HCl. Tricarbonyl(3-allyl-14-η⁴-1,3-pentadiene)iron(0) also undergoes cationic polymerization but the presence of its isomer, tricarbonyl(3-propenyl-14-η⁴-1,3-pentadiene)iron(0) inhibits the polymerization.