Chirality and numbering of substituted tropane alkaloids

The strict application of IUPAC rules for the numbering of tropane alkaloids is not always applied by authors and there is hence a lot of confusion in the literature. In most cases, the notation of 3, 6/7-disubstituted derivatives has been chosen arbitrarily, based on NMR and MS data, without taking into account the absolute configuration of these two carbons. This paper discusses the problem and the relevance of CD and NMR to determine molecular configurations. We report on the use of (1)H-NMR anisochrony (Δδ) induced by the Mosher's chiral auxiliary reagents (R)-(-)- and (S)-(+)-α-methoxy-α-trifluoromethyl-phenylacetyl chlorides (MTPA-Cl), to determine the absolute configuration of (3R,6R)-3α-hydroxy-6β-senecioyloxytropane, a disubstituted tropane alkaloid isolated from the aerial parts of Schizanthus grahamii (Solanaceae). These analytical tools should help future works in correctly assigning the configuration of additional 3, 6/7 disubstituted tropane derivatives.     

Fatigue Effects in Elastic Materials with Variational Damage Models: A Vanishing Viscosity Approach

Journal of Nonlinear Science - We study the existence of quasistatic evolutions for a family of gradient damage models which take into account fatigue, that is the process of weakening in a...     

Density matrix of crystalline systems. II. The influence of structural and computational parameters

The one-electron density matrix (DM ) of a number of crystalline systems—lithium, graphite, boron nitride, silicon, and beryllium—are considered here, as resulting from Hartree–Fock–SCF-LCAO calculations. The influence of structural and computational parameters is discussed. It is shown in particular why the structure of chemical bonds in semiconductors leads to an oscillating long-range behavior of the DM , similar to that observed in metals, where these oscillations are related to the very existence of a Fermi surface. Concerning computational parameters, the influence of the density of sampling k points and of basis set on the calculated DM is considered; it is shown that the choice of the basis set is not a very critical one as far as the DM range is concerned. Some critical aspects of the interrelation between DM range and exchange part of the Fock Hamiltonian are analyzed.     

Rate coefficients and mechanisms of the reaction of cl‐atoms with a series of unsaturated hydrocarbons under atmospheric conditions

Rate coefficients and/or mechanistic information are provided for the reaction of Cl‐atoms with a number of unsaturated species, including isoprene, methacrolein ( MACR ), methyl vinyl ketone ( MVK ), 1,3‐butadiene, trans‐2‐butene, and 1‐butene. The following Cl‐atom rate coefficients were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 ± 0.6) × 10^?10cm³ molecule^?1 s^?1 (independent of pressure from 6.2 to 760 Torr); k( MVK ) = (2.2 ± 0.3) × 10^?10 cm³ molecule^?1 s^?1; k( MACR ) = (2.4 ± 0.3) × 10^?10 cm³ molecule^?1 s^?1; k(trans‐2‐butene) = (4.0 ± 0.5) × 10^?10 cm³ molecule^?1 s^?1; k(1‐butene) = (3.0 ± 0.4) × 10^?10 cm³ molecule^?1 s^?1. Products observed in the Cl‐atom‐initiated oxidation of the unsaturated species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH₂O (9.5 ± 1.0%), HCOCl (5.1 ± 0.7%), and 1‐chloro‐3‐methyl‐3‐buten‐2‐one (CMBO, not quantified) from isoprene; chloroacetaldehyde (75 ± 8%), CO₂ (58 ± 5%), CH₂O (47 ± 7%), CH₃OH (8%), HCOCl (7 ± 1%), and peracetic acid (6%) from MVK ; CO (52 ± 4%), chloroacetone (42 ± 5%), CO₂ (23 ± 2%), CH₂O (18 ± 2%), and HCOCl (5%) from MACR ; CH₂O (7 ± 1%), HCOCl (3%), acrolein (≈3%), and 4‐chlorocrotonaldehyde (CCA, not quantified) from 1,3‐butadiene; CH₃CHO (22 ± 3%), CO₂ (13 ± 2%), 3‐chloro‐2‐butanone (13 ± 4%), CH₂O (7.6 ± 1.1%), and CH₃OH (1.8 ± 0.6%) from trans‐2‐butene; and chloroacetaldehyde (20 ± 3%), CH₂O (7 ± 1%), CO₂ (4 ± 1%), and HCOCl (4 ± 1%) from 1‐butene. Product yields from both trans‐2‐butene and 1‐butene were found to be O₂‐dependent. In the case of trans‐2‐butene, the observed O₂‐dependence is the result of a competition between unimolecular decomposition of the CH₃CH(Cl)? CH(O?)? CH₃ radical and its reaction with O₂, with k_decomp/k_O2 = (1.6 ± 0.4) × 10¹⁹ molecule cm^?3. The activation energy for decomposition is estimated at 11.5 ± 1.5 kcal mol^?1. The variation of the product yields with O₂ in the case of 1‐butene results from similar competitive reaction pathways for the two β‐chlorobutoxy radicals involved in the oxidation, ClCH₂CH(O?)CH₂CH₃ and ?OCH₂CHClCH₂CH₃. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 334–353, 2003     

Evidence of nuclear motion in H<Subscript>2</Subscript>-like molecules by means of high harmonic generation

The dynamics of hydrogen-like molecules is investigated beyond the usual fixed nuclei approximation. The nuclear motion introduces in the familiar spectrum of emitted radiation additional regular lines whose separation is essentially given by the vibrational frequency of nuclear motion. A wavelet analysis of the emitted spectrum shows that the intensity of the harmonic lines is modulated with the same period of the nuclear motion; this suggests the possibility of the real-time control of the nuclear dynamics.     

Fourier transform infrared spectrum of the ν3 band of HCO

The ν₃ fundamental band of the formyl radical, HCO, in the 5.3-μm region has been observed at high resolution (0.0025 cm⁻¹, unapodized) using a Fourier transform spectrometer. The HCO radicals were formed by the reaction of F atoms with H₂CO in a fast-flow multiple-traversal absorption cell. A total of 298 lines were measured with an accuracy of about 0.0004 cm⁻¹ and assigned to transitions with values of the rotational quantum numbers N and K_a up to 20 and 5, respectively. These data greatly improve the knowledge of the HCO ν₃ line positions and (v₁v₂v₃) = (001) vibrational state molecular parameters as compared to earlier laser magnetic resonance studies of this band, especially for higher values of N. The ν₁ fundamental band of HCO was also observed and an analysis of these data agrees well with the recent study of Dane et al. [J. Chem. Phys. 88, 2121–2128 (1988)].     

Pair production at strong coupling in weak external fields

The rate of electron-positron pair production in a weak external electric field at large values of e is computed. The method is extended to compute the rate of monopole-antimonopole pair production in a weak external magnetic field at large magnetic charge.     

The role of excitons and substrate temperature in low-energy (5–50 eV) electron-stimulated dissociation of amorphous D2O ice

We have studied the interaction of low-energy (5–50 eV) electrons with nanoscale (10 ML) ice films by probing the yields and quantum-state distributions of the neutral dissociation products using laser resonance-enhanced multiphoton ionization spectroscopy. In particular, we have observed the electron-stimulated desorption (ESD) of D (²S), O (³P₂) and O (¹D₂) from amorphous D₂O films. These products are observed at threshold energies (relative to the vacuum level) between 6.5–7 eV and desorb with low kinetic energies (60–85 meV) which are independent of the incident electron energy. We associate the ESD of atomic fragments from ice with dissociation of Frenkel-type excitons of 4a₁ character which are near the bottom of the ice conduction band. These excitons are created either directly or via electron-ion recombination. Changing the surface temperature from 88 to 145 K results in an increase in the thermal component of the time-of-flight (kinetic energy) distributions and an overall increase in the neutral fragment yield. We suggest that the change in neutral yield with substrate temperature results from a combination of: (1) increased electron-ion recombination; (2) exciton transport to the near-surface region; and (3) dissociation followed by inelastic scattering and desorption.     

Gravitational anomalies and the family's index theorem

We discuss the use of the family's index theorem in the study of gravitational anomalies. The geometrical framework required to apply the family's index theorem is presented and the relation to gravitational anomalies is discussed. We show how physics necessitates the introduction of the notion oflocal cohomology which is distinct from the ordinary topological cohomology. The recent results of Alvarez-Gaumé and Witten are derived by using the family's index theorem.This work was supported in part by the National Science Foundation under Contracts PHY81-18547 and MCS80-23356; and by the Director, Office of High Energy and Nuclear Physics of the US Department of Energy under Contracts DE-AC03-76SF00098 and AT0380-ER10617Alfred P. Sloan Foundation Fellow     

Chiral ward identities,effective actions and meson-glueball mixing

The low-energy spectrum of 1⁺ and 0^? mesons in one-flavour QCS is investigated. It is shown that there exist two light pseudoscalar mesons, which are linear combinations of pure quark and pure glueball states. Simple relations implied by the axial anomaly for their decay constants are confirmed. The mass generation mechanism for the lightest pseudoscalar meson is identified as due to the mixing of the operators $\text{i}\text{ψ}\text{γ}{}_5\text{ψ}$ and $\text{(?}\text{g}{}^2\text{16π}{}^2\text{)}{}^1\text{F}{}_{\mathrm{\mu \nu }}{}^{\mathrm{a}}\text{F}{}^{\mathrm{a\mu \nu }}$, and the U(1) problem in this model is resolved. To establish these results, new functional methods are developed to determine the effective action for the appropriate fields in a low-energy approximation. A novel feature of our work is the introduction of a “symmetric” effective action, defined using a non-standard Legendre transform. The anomalous chiral Ward identities imply a simple invariance property for this functional, enabling it to be constructed in a particularly systematic way. Finally, the relation of our general results to the literature on effective lagrangians in the $\text{1}\text{N}$ approximation is discussed.