Synthesis of sterically hindered 1-arylpyrrolidines and 1-arylpiperidines by condensation of primary aromatic amines with cyclic ethers or diols

A variety of 1-($\text{o}$-alkylphenyl)- and 1-($\text{o}$-$\text{o}$'-dialkylphenyl)- pyrrolidines and -piperidines were prepared by the gas phase alumina mediated condensation of tetrahydrofuran (THF), tetrahydropyran (THP) or the corresponding diols with primary aromatic amines in fair to high yield. This methodology can also be used for the synthesis of 1-phenylhexahydroazepine from aniline. A mechanistic interpretation of the catalytic action of alumina is presented.     

A Molecular Analogue of the C−H Activation Intermediate of the Silica-Supported Ga(III) Single-Site Propane Dehydrogenation Catalyst: Structure and XANES Signature

Propane dehydrogenation is an important field of research due to an increasing world-wide demand of propene while classical production routes through naphtha cracking are in decline. In that context, silica-supported Ga(III) sites, synthesized from surface organometallic chemistry principles, show high selectivity and stability in the propane dehydrogenation reaction. This performance is in significant contrast to the reported fast deactivation and lower selectivity of most Ga₂O₃ and CrO₃ based materials. The Ga-catalyzed propane dehydrogenation reaction is proposed to proceed through the formation of Ga alkyl intermediates for which it would be desirable to have detailed structural and spectroscopic information. Here, we prepare a consistent series of Ga(III) molecular complexes with varying numbers of alkyl and siloxide ligands; they are characterized by single crystal X-Ray diffraction and X-Ray Absorption Near Edge Structure analysis, which is known to be highly sensitive to the Ga coordination environment. We report in particular the structure and the spectroscopic signatures of [Ga(ⁱPr)(OSi(O^tBu)₃)₂(HOSi(O^tBu)₃)], a molecular mimic of the key proposed reaction intermediates in the Ga-catalyzed PDH reaction.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

On the Motion of a Dynamic System with Minimal Dissipation

The motion of a holonomic scleronomic non-conservative mechanicalsystem with minimal dissipation is considered. As applicationsof the theory several problems are studied in detail.     

The conjugate-pairing rule for non-Hamiltonian systems

In systems that satisfy the Conjugate Pairing Rule (CPR), the spectrum of Lyapunov exponents is symmetric. The sum of each conjugate pair of exponents is identical. Since in dissipative systems the sum of all the exponents is the entropy production divided by Boltzmann's constant, the calculation of transport coefficients from the Lyapunov exponents is greatly simplified in systems that satisfy CPR. Sufficient conditions for CPR are well known: the underlying adiabatic dynamics should be symplectic. However, the necessary conditions for CPR are not known. In this paper we report on the results of computer simulations which shed light on the necessary conditions for the CPR to hold. We provide, for the first time, convincing evidence that the standard molecular dynamics algorithm for calculating shear viscosity violates the CPR, even in the thermodynamic limit. In spite of this it appears that the sum of the maximal exponents is equal to the entropy production per degree of freedom. Thus it appears that the shear viscosity can still be calculated using the standard viscosity algorithm by summing the maximal pair of exponents.(c) 1998 American Institute of Physics.     

Monomeric Copper(II) Sites Supported on Alumina Selectively Convert Methane to Methanol

Monomeric Cu^II sites supported on alumina, prepared using surface organometallic chemistry, convert CH₄ to CH₃OH selectively. This reaction takes place by formation of CH₃O surface species with the concomitant reduction of two monomeric Cu^II sites to Cu^I, according to mass balance analysis, infrared, solid‐state nuclear magnetic resonance, X‐ray absorption, and electron paramagnetic resonance spectroscopy studies. This material contains a significant fraction of Cu active sites (22 %) and displays a selectivity for CH₃OH exceeding 83 %, based on the number of electrons involved in the transformation. These alumina‐supported Cu^II sites reveal that C?H bond activation, along with the formation of CH₃O‐ surface species, can occur on pairs of proximal monomeric Cu^II sites in a short reaction time.     

Field testing of biological spectral weighting functions for induction of UV-absorbing compounds in higher plants

Action spectra are typically used as biological spectral weighting functions (BSWF) in biological research on the stratospheric ozone depletion issue. Despite their critical role in determining the amount of UV supplied in experiments, there has been only limited testing of different functions under realistic field conditions. Here, we calculate effective radiation according to five published BSWF and evaluate the appropriateness of these BSWF in representing the induction of UV-absorbing compounds. Experiments were carried out in the field using both ultraviolet-B radiation (280-320 nm) supplementation and selective filtering of solar UV radiation. For the four species tested, BSWF that extend into the ultraviolet-A radiation (320-400 nm) (UV-A) with moderate effectiveness best represented the observed results. When compared with the commonly used generalized plant response, these BSWF suggest that simulations of ozone depletion will require more radiation than in the past experiments. However, they imply lower radiation supplements than a new plant growth BSWF that has a greater emphasis on UV-A wavelengths.     

Wall mediated transport in confined spaces: exact theory for low density

We present a theory for the transport of molecules adsorbed in slit and cylindrical nanopores at low density, considering the axial momentum gain of molecules oscillating between diffuse wall reflections. Good agreement with molecular dynamics simulations is obtained over a wide range of pore sizes, including the regime of single-file diffusion where fluid-fluid interactions are shown to have a negligible effect on the collective transport coefficient. We show that dispersive fluid-wall interactions considerably attenuate transport compared to classical hard sphere theory.     

Different approaches for evaluating exponentially weighted nonequilibrium relations

The Kawasaki identity (KI) and the Jarzynski equality (JE) are important nonequilibrium relations. Both of these relations take the form of an ensemble average of an exponential function and can exhibit convergence problems when the average of the exponent differs greatly from the log of the average of the exponential function. In this work, we re-express these relations so that only selected regions need to be evaluated in an attempt to avoid these convergence issues. In the context of measuring free energies, we compare our method to the JE and the literature standard approach, the maximum likelihood estimator (MLE), and show that in a system with asymmetric work distributions it can perform as well as the MLE. For the KI, we derive an analog to the MLE to compare with our relation and show that these two new relations improve on the KI and are complimentary to each other.