Formation and fragmentation of the [M + Na]+ ion of glycosides in fast atom bombardment mass spectrometry

Positive-ion fast atom bombardment (FAB) mass spectra of flavonol and steroid glycosides with sodium chloride added showed well known characteristic features; of the appearance of [M + Na]⁺ peaks, disappearance of [M + H]⁺ peaks and a significant decrease in the peak heights of fragment ions. Compared with the features in the FAB mass spectra of crown ethers with addition of salt, and above features suggest a complexation between Na⁺ and the glycosides in matrix solution. The B/E-constant linked scanning technique was used to obtain structural information of the [M + Na]⁺ ion of the glycosides. The B/E spectra gave the daughter-ion peaks, suggesting that coordination of Na⁺ with the biosides and triosides occurs at the sugar moiety, whereas the coordination with the monoglycosides occurs at the aglycone moiety, except for monoglycosides in which the aglycone moiety does not contain significant oxygen functional groups such as OH and CO.     

Adsorption of CO on a Pt electrode in acidic solution: Ir-acttve and -inactive CO'S adsorbed in the double-layer region

Carbon monoxide adsorbed on a smooth platinum electrode in the double-layer region was investigated in 1 M HClO₄ solution by using in situ polarization modulation IR reflection spectroscopy and an electrochemical oxidation. From the electrochemical oxidation, the adsorbed CO could be distinguished to be comprised of stable and unstable adsorbed CO's. The unstable adsorbed CO constituted about of the adsorbed CO, and corresponded to linearly adsorbed CO, but the band intensity of the linearly adsorbed CO was not proportional to the amount of unstable adsorbed CO. The stable adsorbed CO constituted about ; it was one-site adsorbed, and was an IR-inactive species. It is presumed that the IR-inactive species is adsorbed on two Pt atoms with the C-O axis parallel to the electrode surface and one of the Pt atoms bound to two CO molecules.     

Anomalous diffusion of hydrogen in β-VHx: Pulsed-NMR experiments on H1

Diffusion of hydrogen atoms in β-VH_x has been studied by means of a pulsed-NMR technique. A large temperature dependence of the activation energy towards the phase transition temperature βα has been noted, and is interpreted in terms of a saddle point energy and the energy of stabilization of c-octahedral sites relative to other sites.     

Structures of three crystal modifications of poly(3,3-dimethyloxacyclobutane)

Three crystal modifications of poly(3,3-dimethyloxacyclobutane) [? CH₂C(CH₃)₂CH₂O? ]_n were found and their structures were analyzed by x-ray diffraction. Modification I is obtained only under tension and disappears on relaxing the tension. From the fiber period of 4.83 Å, the molecular structure seems to be planar zigzag. In modification II, two chains in T₃GT₃? conformation pass through a monoclinic cell with parameters a = 8.93 Å, b = 7.48 Å, c (fiber axis) = 8.35 Å, β = 97.9°, and the space group P2₁/c-C. In modification III, two (T₂G₂)₂ chains pass through an orthorhombic cell with parameters a = 15.60 Å, b = 5.74 Å, c (fiber axis) = 6.51 Å, and the space group, C222₁–D. Molecular conformations of the three crystal modifications correspond to those of polyoxacyclobutane.     

On the radiation-induced polyaddition of bisperfluoroisopropenyl terephthalate with 1,4-dioxane

Radical polyaddition of bis(α-trifluoromethyl-β,β-difluorovinyl)terephthalate [CF₂C(CF₃)OCOC₆H₄COOC(CF₃)CF₂] (BFP) with 1,4-dioxane (DOX) afforded higher molecular weight polymers under γ-rays radiation from a source when compared to those yielded by benzoyl peroxide initiation. More detailed study on the radiation-induced polyaddition of BFP with DOX and optimization of the reaction conditions were carried out. It was necessary to irradiate with doses of 2000, 1500, and 750 kGy, to obtain quantitative conversion of BFP at the feed molar ratios DOX/BFP of 8.0, 16, and 32, respectively. Step-growth polymerization mechanism was suggested by the measurements of molecular weights of the polymers obtained with several irradiation doses. It was concluded that the molecular weight of the polymer could be controlled by the feed molar ratio of DOX/BFP and irradiation doses. The steep increase of molecular weight was observed at the feed molar ratio of DOX/BFP of 8.0 with the irradiation doses above 2000 kGy and the polymer with the weight-average molecular weight of 2.36×10⁴ was obtained with the dose of 3000 kGy. The reaction between polymers might take place after the quantitative conversion of BFP. Radiation-induced radical polyaddition mechanism of BFP with DOX was proposed.     

Palladium-catalyzed transformation of cyclobutanone O-benzoyloximes to nitriles via C-C bond cleavage

Palladium-catalyzed transformation of cyclobutanone O-benzoyloximes to a variety of nitriles is described. The reaction may proceed via two important steps, that is, (i) oxidative addition of the N-O bond of oximes to Pd(0) to give a cyclobutylideneaminopalladium(II) species and (ii) beta-carbon elimination of this species to afford a reactive alkylpalladium species. The kind of products is very dependent on the nature of substituents on the cyclobutane ring. The direction of the C-C bond cleavage is controlled by the kind of ligand employed. The sequential reaction composed of the C-C bond cleavage and the subsequent intra- and intermolecular C-C bond formations via the corresponding alkylpalladium species is also demonstrated. For example, an oxime having an alkynyl moiety at a suitable position reacts with a variety of alkenes to afford nitriles bearing dienylcyclopentane moiety in moderate to good yields.     

Facile and catalytic degradation method of DDT using Pd/C-Et3N system under ambient pressure and temperature

The catalytic degradation method of p,p′-DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane] and its regioisomer o,p′-DDT [1,1,1-trichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl)ethane] using the Pd/C-Et₃N system under ambient hydrogen pressure and temperature was established. The presence of Et₃N was necessary for the quick and complete breakdown of DDT. The independent degradation study of two intermediates, p,p′-DDD [2,2-bis(p-chlorophenyl)-1,1-dichloroethane] and p,p′-DDE [2,2-bis(p-chlorophenyl)-1,1-dichloroethylene] using GC-MS let us to speculate the degradation pathway of p,p′-DDT. In the initial phase of the reaction, p,p′-DDT degradation splits into two ways: a dehydrochlorination pathway and a hydrodechlorination pathway. In each pathway, reaction starts from an aliphatic moiety and subsequent hydrodechlorination from the benzene moieties takes place in a stepwise manner. The former pathway leads to the formation of 1,1-diphenylethane and the latter leads to the formation of 1,1-dichloro-2,2-diphenylethane. These diphenylethane analogs, which are less toxic compared with p,p′-DDT, are terminal degradation products in our system. The distinctive features of our catalytic degradation method of DDTs are reliability, simplicity, efficiency, and inexpensiveness.     

A sharp transition for the two-dimensional Ising percolation

We show that the percolation transition for the two-dimensional Ising model is sharp. Namely, we show that for every reciprocal temperature >0, there exists a critical valueh _c () of external magnetic fieldh such that the following two statements hold.

Impedance spectra analysis of thermoresponsive poly(acryloyl‐L‐proline methyl ester) gel membrane in LiCl solution

Impedance spectra analysis of a thermoresponsive poly(acryloyl‐L ‐proline methyl ester) (poly(A‐ProOMe)) hydrogel membranes in an aqueous solution of LiCl was carried out using a simple equivalent model. The hydrogel membrane was synthesized by γ‐radiation‐induced polymerization and crosslinking of A‐ProOMe monomer aqueous solution in a glass‐cast. By means of the impedance spectra analysis, a novel method for the calculation of the ionic conductivity of the hydrogel membranes in LiCl solution was proposed. The calculated ionic conductivity was in agreement with the determined value. In addition, effects of temperature and LiCl concentration on the impedance spectra and ionic conductivity of the gel membrane were analyzed. Results indicated that the impedance spectra analysis is a very useful tool for evaluating the electric properties of gel membranes in an electrolyte solution. The poly (A‐ProOMe) gel membrane in 1.0 M LiCl solution showed a high ionic conductivity of about 0.2 S/cm at 14 °C. The temperature‐dependence of the ionic conductivity was a complex nonlinear form due to the volume phase transition of the thermoresponsive poly(A‐ProOMe) gel membrane, and the volume phase transition temperature appeared to be decreased with the increase in the LiCl concentration. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2843–2851, 2005