Molecular structure and puckering potential of gas-phase 1-pyrroline as determined by microwave and infrared spectroscopy

The microwave spectrum of 1-pyrroline has been measured from 8 to 48 GHz. The transitions have been assigned to those of the ground state and the four lowest excited states of the ring-puckering vibration of monomer, which is a five-membered ring molecule with one CN double bond. The trimer, which exists in the liquid phase, has not been detected in the gas phase. The geometrical structure of the monomer has been estimated by an ab initio calculation and the trimer by a molecular mechanics calculation. The former is consistent with the experimental rotational constants. A gas-phase infrared spectrum has also been measured, and the ring-puckering potential has been determined by an analysis of the combination bands of the ring-puckering mode and the ring-stretching modes. The potential is described using a puckering coordinate, z, as V(z) = az² + bz⁴, where $\text{a = ?3.358(16) × 10}{}^4\text{cm}{}^{\mathrm{?1}}\text{A}\text{?}{}^{\mathrm{?2}}$ and $\text{b = 1.345(9) × 10}{}^6\text{cm}{}^{\mathrm{?1}}\text{A}\text{?}{}^{\mathrm{?4}}$; these values are intermediate of the corresponding values for cyclopentene and 1-pyrazoline. The nuclear quadrupole coupling constants, χ_aa = ?4.39(10), χ_bb = 1.04(10), and χ_cc = 3.35(10) MHz, have been determined by an analysis of well-resolved hyperfine splittings. These constants have been reproduced by an ab initio calculation with a 4-31G(N¹) basis set.     

Analysis of sodium alkylsulphonates using filament heated in-beam electron impact mass spectrometry

Summary By means of the filament heated in-beam method at 280–450° C, the series of sodium alkylsulphonates (RSO₃Na, where R=C₂H₅ to n-C₁₂H₂₅) give very simple mass spectra: Na⁺, [RSO₃Na₂]⁺, which is the base peak except for R=n-C₄H₉, [(RSO₃)₂Na₃]⁺ and, in most cases, [(RSO₃)₃Na₄]⁺. Fragmentations other than these three or four peaks are observed only in the case of n-heptylsulphonate. The proposed method of analysis for simple alkylsulphonic acids is applicable to ordinary electron-impact mass spectrometers.

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Analyse von Natrium-alkylsulfonaten durch Elektronenstoß-Massenspektrometrie mit Probenerhitzung im Elektronenstrahl

Zusammenfassung Mit Hilfe dieser Methode (280–450° C) erhält man für Natriumalkylsulfonate (RSO₃Na mit R=C₂H₅ bis n-C₁₂H₂₅) sehr einfache Massenspektren: Na⁺, [RSO₃Na₂]⁺ (Basispeak mit Ausnahme von R=n-C₄H₉), [(RSO₃)₂Na₃]⁺ und in den meisten Fällen [(RSO₃)₃Na₄]⁺. Andere Fragmentierungen als diese 3 oder 4 Peaks wurden nur bei n-Heptylsulfonat beobachtet. Dieses Verfahren zur Analyse einfacher Alkylsulfonsäuren ist für übliche Elektronenstoß-Massenspektrometer verwendbar.

     

Synthetic studies on carbapenem antibiotics from penicillins.II. regio- and stereoselective aldol reaction of a chiral azetidinone: a synthesis of optically active 6-epicarpetimycins

Aldol and alkylation reactions of the chiral 4-allylazetidinone 1 gave 3,4-trans-azetidinones as major products, in which 10 was converted in several steps to the optically active 6-epicarpetimycins 2.     

Modified graessley theory for non-newtonian viscosities of polydimethylsiloxanes and their solutions

A deviation from Graessley's theory of entanglement viscosity appears at very high shear rates when the flow of polydimethylsiloxanes of various molecular weights and their solutions with various concentrations is measured by the capillary method. In order to explain this deviation, a modified Graessley theory is proposed according to the previously reported suggestion that frictional viscosity appears not to be negligible at high shear rates. A reducing procedure taking a frictional viscosity parameter into account was performed. All of the reduced data are combined to give a master curve in spite of a wide range of molecular weight, concentration, and shear rate (from the lower Newtonian to very highest non-Newtonian flow region). The findings from the reducing procedure completely explain the mechanism of non-Newtonian flow for the bulk polymers with various molecular weights, including those below the critical molecular weight for entanglement, and for polymer solutions at any concentration. The viscosity of the linear polymer system consists of the shear-dependent entanglement term η_ent proposed by Graessley and the shear-independent frictional term η_fric. The non-Newtonian behavior depends on the ratio of η_ent/η_fric at the shear rate of measurement. The ratio of zero-shear entanglement viscosity η_ent,0 to η_fric and the critical shear rate for onset of the non-Newtonian flow may be used as a measure of the non-Newtonian behavior of the system and a measure of capability for its rising, respectively. The Graessley theory is to be included in the present modified theory and is applicable to the case of η_entη_fric ? 1.     

Critical molecular weight for onset of non-newtonian flow and upper newtonian viscosity of polydimethylsiloxane

The flow curves of fractionated polydimethylsiloxanes of different molecular weights were obtained over a wide range of shear rates, from 3 × 10^?1 to 4.3 × 10⁶ sec^?1, by use of a gas-driven capillary viscometer designed to decrease the experimental error in high shear rate region. Non-Newtonian flow can occur at molecular weights below the critical molecular weight M_c for the entanglement of polymer chain. The critical molecular weight M′_c for the onset of the non-Newtonian flow is identical with that of the segment of viscous flow. For the polymer of molecular weights from M′_c to M_c, the upper Newtonian viscosity increases with an increase in molecular weight. Above M_c, the upper Newtonian viscosity is almost independent of the molecular weight.     

Synthesis of spirocyclic C-arylribosides via cyclotrimerization

[reaction: see text] Spirocyclic C-arylribosides were synthesized from the known gamma-ribonolactone derivative. Lithium acetylide addition followed by glycosylation with 3-(trimethylsilyl)propargyl alcohol converted the ribonolactone to silylated diynes. After desilylation or iodination, subsequent ruthenium-catalyzed cycloaddition of resultant diynes with alkynes or chloroacetonitrile gave spirocyclic C-arylribosides.     

Determination of structures of cobalt(II)-chloro complexes in hydrochloric acid solutions by X-ray absorption spectroscopy at 298 K

The anion exchange reaction is fundamental to the adsorption and desorption of a specific species from a solution phase to an extracting phase, and it is widely used for separation and waste fluid treatment in industrial fields. However, the details of the anion exchange reaction are poorly understood. Quantitative thermodynamic analysis needs a precise solution condition before and after the exchange reaction. Identification of species adsorbed on the anion exchanger is also necessary because there are multiple species in the solution phase in general. Cobalt is a base metal that is widely used in modern society. One of the authors determined the distribution of cobalt-chloro complexes in hydrochloric acid solutions. It is necessary to know what species are adsorbed on anion exchangers for the thermodynamic analysis of the anion exchange reaction. The comparison in structures between the species in the solution phase and adsorbed on anion exchangers reveals what species are adsorbed. Therefore, the determination of the structures of cobalt-chloro complexes in the solution phase is the next step for quantitative analysis. X-ray absorption spectroscopy (XAS) was used for the structure analysis. Factor analysis can decompose extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectra consisting of multiple species into individual spectra of single species using the distribution determined using UV-Vis absorption spectra. Fitting EXAFS theoretical models to the decomposed individual spectra determined the structures of three cobalt-chloro complexes: an octahedron of [Co^II(H₂O)₆]²⁺, a distorted octahedron of [Co^II(H₂O)₅Cl]⁺, and a tetrahedron of [Co^IICl₄]^2?. The XANES spectra showed us that the Cl ligand in [Co^II(H₂O)₅Cl]⁺ was attracted to the center atom of Co^II by an electrostatic force, and the bonding system between Cl ligands and Co^II in [Co^IICl₄]^2? involved covalency.

     

Electron-boson coupling and oxygen-isotope effect in the optical conductivity of high-Tc superconductors

We have investigated electron-boson coupling in the optical conductivity of high-T_c superconductors through the optical self-energy. The real part of the self-energy (ReΣ^op(ω)) of YBa₂Cu₃O_y (YBCO) shows a characteristic doping dependence. In the optimally doped YBCO, ReΣ^op(ω) has a single peak around 65 meV, which corresponds to the kink structure of the band dispersion. On the other hand, in the under-doped YBCO, the peak structure of ReΣ^op(ω) splits into two parts. To evaluate contribution from the phonons in electron-boson coupling, we have measured oxygen-isotope effects by substituting ¹⁶O→¹⁸O for the optimally doped and under-doped YBCO.     

Thermal conductivity evidence for a dx2-y2 pairing symmetry in the heavy-fermion CeIrIn5 superconductor

The phase diagram of the quasi-2D Ce(Ir,Rh)In5 system contains two distinct superconducting domes. By the thermal transport measurements in rotating magnetic fields H, we pinned down the superconducting gap structure of CeIrIn5 in the second dome, located distant from the first dome in proximity to an antiferromagnetic quantum critical point. Clear fourfold oscillation was observed when H is rotated within the ab plane, while no oscillation was observed within the bc plane. In sharp contrast to previous reports, our results are most consistent with dx2-y2 symmetry, implying that the superconductivity in the second phase is also mediated by antiferromagnetic spin fluctuations.