Probing the CH⋅⋅⋅π Weak Hydrogen Bond in Anesthetic Binding: The Sevoflurane–Benzene Cluster

Cooperativity between weak hydrogen bonds can be revealed in molecular clusters isolated in the gas phase. Here we examine the structure, internal dynamics, and origin of the weak intermolecular forces between sevoflurane and a benzene molecule, using multi‐isotopic broadband rotational spectra. This heterodimer is held together by a primary C? H???π hydrogen bond, assisted by multiple weak C? H???F interactions. The multiple nonbonding forces hinder the internal rotation of benzene around the isopropyl C? H bond in sevoflurane, producing detectable quantum tunneling effects in the rotational spectrum.     

Large Amplitude Torsions in Nitrotoluene Isomers Studied by Rotational Spectroscopy and Quantum Chemistry Calculations

Rotational spectra of ortho-nitrotoluene (2-NT) and para-nitrotoluene (4-NT) have been recorded at low and room temperatures using a supersonic jet Fourier Transform microwave (MW) spectrometer and a millimeter-wave frequency multiplier chain, respectively. Supported by quantum chemistry calculations, the spectral analysis of pure rotation lines in the vibrational ground state has allowed to characterise the rotational energy, the hyperfine structure due to the ¹⁴N nucleus and the internal rotation splittings arising from the methyl group. For 2-NT, an anisotropic internal rotation of coupled −CH₃ and −NO₂ torsional motions was identified by quantum chemistry calculations and discussed from the results of the MW analysis. The study of the internal rotation splittings in the spectra of three NT isomers allowed to characterise the internal rotation potentials of the methyl group and to compare them with other mono-substituted toluene derivatives in order to study the isomeric influence on the internal rotation barrier.     

Modulable and Highly Diastereoselective Carbometalations of Cyclopropenes

The copper‐catalyzed carbomagnesiation reaction of cyclopropenyl esters 1 leads to various substituted cyclopropanes species 3 in good yields with very high diastereoselectivities. The reaction proceeds through a syn‐chelated carbomagnesiation reaction and could be extended to various cyclopropenylmethyl ester derivatives 5 . The potential of this approach was illustrated by the preparation of two consecutive all‐carbon quaternary stereocenters. However, the carbometalation reaction needs to be performed at temperature ranging from ?35 to ?20 °C to avoid subsequent fragmentation reaction into stereodefined β,γ‐nonconjugated unsaturated esters 4 . Alternatively, the carbocupration reaction with organocopper species could also be performed to leads to configurationally stable cyclopropyl copper species 2[Cu] . Additionally, when the Lewis acid character of the copper center is decreased (i.e., RCuCNLi), the reaction proceed with an anti‐selectivity. The diastereodivergent behavior of these organometallic species is of synthetic interest, since both diastereomers syn‐ 3 and anti‐ 3 can be obtained, at will, from the same precursor cyclopropenyl esters 1 .     

Differentiability of Lipschitz Maps from Metric Measure Spaces to Banach Spaces with the Radon–Nikodym Property

We prove the differentiability of Lipschitz maps X → V, where X denotes a PI space, i.e. a complete metric measure space satisfying a doubling condition and a Poincaré inequality, and V denotes a Banach space with the Radon–Nikodym Property (RNP). As a consequence, we obtain a bi-Lipschitz nonembedding theorem for RNP targets. The differentiation theorem depends on a new specification of the differentiable structure for PI spaces involving directional derivatives in the direction of velocity vectors to rectifiable curves. We give two different proofs of this, the second of which relies on a new characterization of the minimal upper gradient. There are strong implications for the infinitesimal structure of PI spaces which will be discussed elsewhere.     

Model two-dimensional diffraction profiles from disordered vicinal surfaces and random island configurations

Methods for calculating model diffraction profiles of vicinal surfaces and distributions of islands are described. Modeling of rough terrace edges, and of island structures on terraces, has been performed using phenomenological Hamiltonians. The methods are developed for calculating diffraction profiles in all components, s_x, s_z, and s_y, of the momentum transfer. It is s of step structure irregularities is related to profile shape. Qualitative comparison with experiment is made based on the observed characteristics of terraces obtained from STM and LEED data of vicinal Si(OO1).     

Structural studies on banana oil,isoamyl acetate,by means of microwave spectroscopy and quantum chemical calculations

The rotational spectrum of isoamyl acetate, H₃C–COO–(CH₂)₂–CH(CH₃)₂, has been recorded and assigned using a molecular beam Fourier transform microwave (MB-FTMW) spectrometer in the frequency range of 3–26.5?GHz. One conformer has been observed. By comparing the spectroscopic data with the quantum chemical data, it was found that the conformer observed does not have C_s symmetry. The rotational and centrifugal distortion constants were determined. The barrier to internal rotation of the acetate methyl group was found to be 93.98?cm^?1. Due to the high number of the conformers, a systematic nomenclature will be presented.     

A microscopic model for the intrinsic Josephson tunneling in high- superconductors

A quantitative analysis of a microscopic model for the intrinsic Josephson effect in high-temperature superconductors based on interlayer tunneling is presented both within a mean-field BCS evaluation and a numerically essentially exact Quantum Monte-Carlo study. The pairing correlations in the CuO₂-planes are modelled by a 2D Hubbard model with attractive interaction, a model which accounts well for some of the observed features such as the short planar coherence length. The stack of Hubbard planes is arranged on a torus, which is threaded by a magnetic flux. The current perpendicular to the planes is calculated as a function of applied flux (i.e. the phase), and - after careful elimination of finite-size effects due to single-particle tunneling - found to display a sinusoidal field dependence in accordance with interlayer Josephson tunneling. Studies of the temperature dependence of the supercurrent reveal at best a mild elevation of the Josephson transition temperature compared to the planar Kosterlitz-Thouless temperature. These and other results on the dependence of the model parameters are compared with a standard BCS evaluation. Received: 24 February 1998 / Revised: 28 April 1998 / Accepted: 23 June 1998     

Photoconductance of two-dimensional ballistic microstructures

We calculate the photoconductance of two-dimensional ballistic microstructures subject to a high-frequency electromagnetic field. First, we study a simple quantum point contact. Absorption of photons is due to electronic transitions between different modes. A transition between a propagating and a nonpropagating mode results effectively in a backscattering process, and gives a negative or positive contribution to the current, depending on the gate voltage; the total quantized conductance acquires an additional, quite pronounced step-structure. Then, we demonstrate a new effect where the electron-photon interaction in a structure of slightly more complex geometry plays the same role as impurity scattering does in a “dirty” system. All relevant photons of the external electromagnetic field are coherent and spatial interference effects in electron-photon scattering become possible in spite of the inelastic nature of the collisions. These interference effects can be controlled by the gate voltage or the frequency of the electromagnetic field. As an illustration we calculate the photoconductance of a double point-contact geometry.