Chromatographic deuterium isotope effects of derivatized N-glycans and N-glycopeptides in a zwitterionic type of hydrophilic interaction chromatography

HPLC/MS is now an essential method for the analysis of glycans and glycopeptides. A technique using ICATs is also becoming popular for their comparative/quantitative analysis based on MS signal intensities. However, the RP HPLC most often used causes "doublet" peaks of deuterium-labeled and nonlabeled peptides, which are well known for causing the chromatographic deuterium isotope effect. Such doublet peaks are undesirable for precise comparison of MS signal intensities. This report shows that, in the zwitterionic type of hydrophilic interaction chromatography, the chromatographic deuterium isotope effect is negligibly small for N-glycans derivatized with deuterium-labeled 2-aminopyridine and N-glycopeptides derivatized with deuterium-labeled succinic anhydride.     

Mechanism of [gamma-H2SiV2W10O40](4-)-catalyzed epoxidation of alkenes with hydrogen peroxide

The mechanism of [gamma-H2SiV2W10O40]4--catalyzed epoxidation of alkenes with hydrogen peroxide in acetonitrile/tert-butyl alcohol was investigated. The negative Hammett rho+ (-0.88) for the competitive oxidation of p-substituted styrenes and the low XSO (XSO = (nucleophilic oxidation)/(total oxidation)) value of <0.01 for the [gamma-H2SiV2W10O40]4--catalyzed oxidation of thianthrene-5-oxide reveal that the strong electrophilic oxidant species is formed on [gamma-H2SiV2W10O40]4- (I). The preferable formation of trans-epoxide for the epoxidation of 3-substituted cyclohexenes shows the steric constraints of the active oxidant on I. The 51V NMR, 183W NMR, and CSI-MS spectroscopy show that the reaction of I with hydrogen peroxide leads to the reversible formation of a hydroperoxo species [gamma-HSiV2W10O39OOH]4- (II). The successive dehydration of II forms III, which possibly has an active oxygen species of a mu-eta2:eta2-peroxo group. The kinetic and spectroscopic studies show that the present epoxidation proceeds via III. The energy diagram of the epoxidation with density functional theory (DFT) supports the idea.     

QSAR and mode of action studies of insecticidal ecdysone agonists

A series of our SAR and QSAR studies of synthetic moulting hormone agonists, dibenzoylhydrazines (DBH), exhibiting insecticidal/larvicidal activity are reviewed in this article. We prepared a number of analogues where various substituents are introduced into the two benzene rings of DBH and measured their biological activity using various biological systems. Larvicidal activity was against larvae of the rice stem borer Chilo suppressalis and the moulting hormone activity was in terms of the stimulation of N-acetylglucosamine incorporation in a cultured integument system of the same insect species. Binding affinity to the ecdysone receptor was assayed with intact Sf-9 cell lines in which the ADME processes are negligible as well as using receptor proteins obtained by in vitro translation of the responsible cDNA cloned from cell-free preparation of integumentary tissue of C. suppressalis. Variations in the biological activity indices were either correlated between two types of activity or correlated using physicochemical molecular and substituent parameters in terms of the classical QSAR. Comparisons among correlations and with recently revealed X-ray crystallographic findings clearly indicate the physicochemical meaning of parameters significant in the correlation equations to help understanding molecular mechanism of the moulting hormonal action.     

Development and flow evaluation of electro-rheological nano-suspensions

An attempt has been made to develop a candidate for electro-rheological (ER) nano-suspensions based on anatase titanium dioxide with a particle diameter around 300 nm. The micro-gap flow behavior and microstructure were evaluated for a suspension with a particle volume fraction of 8.8 vol.%. The ER effect was investigated for the nano-suspension. The effect of shearing time on the ER responses was also investigated. The ER effect was discussed in comparison to the effect previously reported for the nano-suspension based on rutile titanium dioxide with a particle diameter around 15 nm.     

Allylation of alcohols and carboxylic acids with allyl acetate catalyzed by [Ir(cod)2](+)BF4- complex

A facile method for the synthesis of allyl alkyl ethers from alcohols with allyl acetate was developed by the use of [Ir(cod)(2)](+)BF(4)(-) complex. For instance, the reaction of allyl acetate with n-octyl alcohol in the presence of a catalytic amount of [Ir(cod)(2)](+)BF(4)(-) complex afforded allyl octyl ether in quantitative yield. Allyl carboxylates were also prepared by the exchange reaction between carboxylic acids and allyl acetate in good yields. The [Ir(cod)(2)](+)BF(4)(-) complex catalyzed the reaction of alkyl and aromatic amines with allyl acetate to lead to the corresponding allylamines in fair to good yields.     

Chromium mediated stereoselective synthesis of (Z)-1-fluoro-2-alkenyl alkyl and trialkylsilyl ethers from dibromofluoromethylcarbinyl ethers

Reactions of 2,2-dibromo-2-fluoroethyl alkyl ethers and dibromofluoromethylcarbinyl silyl ethers with CrCl₂ and Mn powder provided 2-fluorovinyl alkyl ethers and 1-fluoro-2-alkenyl enol silyl ethers in high yields and in Z selective manner.     

Chiroptical study of α-aliphatic amino acid films in the vacuum ultraviolet region

A series of natural circular dichroism (CD) and absorption spectra for films of α-aliphatic amino acids--such as alanine, aminobutyric acid, norvaline, norleucine, valine, leucine, and isoleucine--in the vacuum ultraviolet (VUV) region were observed with the absolute values of optical constants at the undulator-based CD beamline TERAS BL5. Preliminary predictions of some CD spectra were also performed, based on quantum-chemical calculations using the crystal structure. Although the absorption spectra show similar features to each other, significant differences between the CD spectra were found, especially in the 7-8 eV region. The CD spectra of aliphatic amino acids with branched alkyl groups in the side-chain--such as valine, leucine, and isoleucine--exhibit strong negative CD peaks in this energy region. In contrast, the corresponding CD peaks were weak or absent in the spectra of amino acids with straight alkyl groups. Our simple calculation, and the absorption spectra of alkanes, suggest that this difference partly originates from the contribution of the alkyl group. Clear discrepancies between the CD spectra of these amino acids in solutions and those in the solid state were also observed; this is probably caused by the different molecular structures in each state. Our results clearly indicated that CD spectra in the VUV region were very sensitive to the conformations of chiral molecules.     

Naucleamides A-E,new monoterpene indole alkaloids from Nauclea latifolia

Five new monoterpene indole alkaloids, naucleamides A-E (1-5), were isolated from the bark and wood of Nauclea latifolia, and the structures and relative stereochemistry were elucidated from the spectroscopic data. Naucleamide E (5) is a unique monoterpene indole alkaloid possessing a pentacyclic ring system with an amino acetal bridge.     

Photodimerization and photooxygenation of 9-vinylcarbazole catalyzed by titanium dioxide and magnesium perchlorate

<正>Photoreaction of 9-vinylcarbazole in acetonitrile in the presence of titanium dioxide and a catalytic amount of magnesium perchlorate gave 3,6-di(9-carbazolyl)-1,2-dioxane as a photooxygenated product via photodimerization of 9-vinylcarbazole.The photoreaction proceeds via an electron transfer mechanism,where magnesium perchlorate accelerated formation of the photo-oxygenated product.     

Metal‐Ion Sensing Europium(III) Complexes with Bidentate Phosphine Oxide Ligands Containing a 2,2′‐Bipyridine Framework

Novel Eu^III complexes with bidentate phosphine oxide ligands containing a bipyridine framework, i.e., [3,3′‐bis(diphenylphosphoryl)‐2,2′‐bipyridine]tris(hexafluoroacetylacetonato)europium(III) ([Eu(hfa)₃(BIPYPO)]) and [3,3′‐bis(diphenylphosphoryl)‐6,6′‐dimethyl‐2,2′‐bipyridine]tris(hexafluoroacetylacetonato)europium(III) ([Eu(hfa)₃(Me‐BIPYPO)]), were synthesized for lanthanide‐based sensor materials having high emission quantum yields and effective chemosensing properties. The emission quantum yields of [Eu(hfa)₃(BIPYPO)] and [Eu(hfa)₃(Me‐BIPYPO)] were 71 and 73%, respectively. Metal‐ion sensing properties of the Eu^III complexes were also studied by measuring the emission spectra of Eu^III complexes in the presence of Zn^II or Cu^II ions. The metal‐ion sensing and the photophysical properties of luminescent Eu^III complexes with a bidentate phosphine oxide containing 2,2′‐bipyridine framework are demonstrated for the first time.