A study of the 220 MHz proton resonance spectra for a series of biologically important acridine-type heterocycles

The high resolution proton magnetic resonance spectra of acridine, phenazine, phenoxazine and phenothiazine have been measured at 220 MHz in various solvents and at several temperatures. Spectra for all four molecules were analyzed iteratively and good agreement was obtained between observed and calculated spectra. Significant differences are noted between the coupling constants and chemical shifts of acridine and phenazine on the one hand and phenoxazine and phenothiazine on the other. These differences are attributed to a nonplanar heterocyclic ring conformation for phenoxazine and phenothiazine in solution. Moreover, it is concluded from the temperature measurements that the heterocyclic rings of phenoxazine and phenothiazine are conformationally flexible in the range covered. Possible mechanisms are suggested for the chemical shift and coupling constant changes.     

The reaction of atomic oxygen O(3P) with propane

The reaction of O(³P) atoms with propanehas been studied at temperatures near 300 K by using a discharge flow system. Oxygen atoms were generated in the absence of molecular oxygen by the reaction N + NO → N₂ + O, nitrogen atoms having been generated in a microwave discharge. Rate constants for the reaction were measured in two ways, either by measurement of O-atom decay in the presence of excess propane or by measuring the change in propane concentration after an appropriate time in the presence of an excess of oxygen atoms. The two methods were in good agreement, and the mean rate constant at 306 K is given by A study of the products of the reaction under conditions corresponding to complete removal of oxygen atoms has shown that an important product of the reaction in the early stages is propene. This is difficult to explain interms of a mechanism involving alkoxy radicals similar to that which has been proposed for some other O(³P)–hydrocarbon reactions. An alternative mechanism is proposed in terms of successive hydrogen abstraction reactions.     

Numerical Simulation of Incompressible Flows Within Simple Boundaries. I. Galerkin (Spectral) Representations

Galerkin (spectral) methods are explored for the numerical simulation of incompressible flows within simple boundaries. A major part of the paper is devoted to the development of transform methods for efficient simulation of flows in box geometries with periodic and free-slip boundary conditions. Techniques for incorporating known symmetries and invariances into transform methods are illustrated for the Taylor-Green vortex. Galerkin methods for accurate and efficient representation of rigid no-slip boundary conditions are also explained. A class of pseudospectral approximations is introduced in order to handle more complicated dynamical interactions in more complicated geometries. Later papers in this series will demonstrate the important advantages of spectral methods over finite-difference methods for simulation of many of the flows of current interest and will present specific numerical results for various transition and turbulent flows.     

Two atom insertions into the silacyclopropane and silacyclopropene rings: mechanistic considerations

Novel two atom insertion reactions into the SiC₂ rings of hexamethylsilirane and 1,1-dimethyl-2,3-bis(trimethylsilyl)-1-silirene involving the C bonds of styrene and α-methylstyrene, 1,3-butadiene and its 2-methyl and 2,3-dimethyl derivatives, and, in the presence of ultraviolet radiation, of aliphatic aldehydes and ketones, are reported. A radical mechanism is suggested tobe operative in these reactions. Also described are novel palladium-catalyzed reactions of the silirene with terminal and internal acetylenes.     

Simulations of proton order and disorder in ice Ih

Computer simulations of ice Ih with different proton orientations are presented. Simulations of proton disordered ice are carried out using a Monte Carlo method which samples over proton degree of freedom, allowing for the calculation of the dielectric constant and for the examination of the degree of proton disorder. Simulations are also presented for two proton ordered structures of ice Ih, the ferroelectric Cmc2(1) structure or ice XI and the antiferroelectric Pna2(1) structure. These simulations indicate that a transition to a proton ordered phase occurs at low temperatures (below 80 K). The symmetry of the ordered phase is found to be dependent on the water potential. The stability of the two proton ordered structures is due to a balance of short-ranged interactions which tend to stabilize the Pna2(1) structure and longer-range interactions which stabilize the Cmc2(1) structure.     

Benchmark calculations of the complete configuration-interaction limit of Born-Oppenheimer diagonal corrections to the saddle points of isotopomers of the H + H2 reaction

We present a detailed ab initio study of the effect that the Born-Oppenheimer diagonal correction (BODC) has on the saddle-point properties of the H3 system and its isotopomers. Benchmark values are presented that are estimated to be within 0.1 cm(-1) of the complete configuration-interaction limit. We consider the basis set and correlation treatment requirements for accurate BODC calculations, and both are observed to be more favorable than for the Born-Oppenheimer energies. The BODC raises the H + H2 barrier height by 0.1532 kcal/mol and slightly narrows the barrier--with the imaginary frequency increasing by approximately 2%.     

Identification by 15N refocused INADEQUATE MAS NMR of intermolecular hydrogen bonding that directs the self-assembly of modified DNA bases

15N solid-state NMR refocused INADEQUATE spectra of two lipophilic deoxyguanosine derivatives unambiguously identify different intermolecular hydrogen-bonding arrangements that are indicative of either guanine ribbon or quartet self-assembly. The observation of guanine quartet formation in the absence of metal ions is a further example that challenges the accepted dogma that quartet formation requires metal ions.     

Efficient batch and continuous flow Suzuki cross-coupling reactions under mild conditions, catalysed by polyurea-encapsulated palladium (II) acetate and tetra-n-butylammonium salts

Suzuki cross-coupling reactions are effected in both conventional organic solvents, under continuous flow conditions at 70 degree C, and in batch mode in supercritical carbon dioxide (scCO2), at temperatures as low as 40 degrees C in the presence of palladium(II) acetate microencapsulated in polyurea [PdEnCat] and tetra-n-butylammonium salts.     

Highlighting gyroscopic motion in crystals in 13C CPMAS spectra by specific isotopic substitution and restricted cross polarization

The temperature-dependent exchange rate and signal coalescence in the 13C CPMAS NMR spectrum of a crystalline molecular gyroscope are exposed by specifically deuterating the overlapping static carbons.