Trialkylammonium salt degradation: implications for methylation and cross-coupling

Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. ¹H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell S_N2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse.

The dual reactivity of N,N,N-trimethylanilinium salts towards arylation and methylation is decoupled in this mechanistic investigation to enable more strategic application of these salts in either reaction class.     

Millimeter-wave arbitrary waveform generation with a direct space-to-time pulse shaper

By using tailored pulse sequences from a novel, 1.5-microm direct space-to-time pulse shaper driving a high-speed photodetector, we have achieved, for the first time to our knowledge, millimeter-wave arbitrary waveform generation at center frequencies approaching 50 GHz. By appropriately designing the driving optical pulse sequences, we demonstrate the ability to synthesize strongly phase- and frequency-modulated millimeter-wave electrical signals on a cycle-by-cycle basis.     

A possible neurophysiological basis of the octave enlargement effect

Although the physical octave is defined as a simple ratio of 2:1, listeners prefer slightly greater octave ratios. Ohgushi [J. Acoust. Soc. Am. 73, 1694-1700 (1983)] suggested that a temporal model for octave matching would predict this octave enlargement effect because, in response to pure tones, auditory-nerve interspike intervals are slightly larger than the stimulus period. In an effort to test Ohgushi's hypothesis, auditory-nerve single-unit responses to pure-tone stimuli were collected from Dial-anesthetized cats. It was found that although interspike interval distributions show clear phase-locking to the stimulus, intervals systematically deviate from integer multiples of the stimulus period. Due to refractory effects, intervals smaller than 5 msec are slightly larger than the stimulus period and deviate most for small intervals. On the other hand, first-order intervals are smaller than the stimulus period for stimulus frequencies less than 500 Hz. It is shown that this deviation is the combined effect of phase-locking and multiple spikes within one stimulus period. A model for octave matching was implemented which compares frequency estimates of two tones based on their interspike interval distributions. The model quantitatively predicts the octave enlargement effect. These results are consistent with the idea that musical pitch is derived from auditory-nerve interspike interval distributions.     

Concerning the Nature of Ionically Modified Aromatic Polyamide Membranes

The application of cross-linking based on ionic bonds has been successfully demonstrated with aromatic polyamides for the improvement of long-term membrane flux stability. Flux decay values, expressed as d log J₁/d log t, have been reduced to -0.02 compared with -0.12 for the untreated membrane control, operating at 102 atms. applied pressure, on a natural seawater feed solution. Selectivity to dissolved inorganic salts such as sodium chloride remains high, for membranes modified in this manner.     

Detection of 17alpha-hydroxyprogesterone caproate in equine plasma by gas chromatography/tandem mass spectrometry

A method was developed for the analysis of the synthetic progestin 17alpha-hydroxyprogesterone caproate in equine plasma following its administration by intramuscular injection. The method employed a reversed-phase solid-phase extraction followed by enol-trimethylsilylation and analysis by gas chromatography/tandem mass spectrometry. The intact ester was detectable in the plasma for up to 2 weeks after a single therapeutic dose, and was found to be stable in equine whole blood for at least 2 months.     

Ab initio calculations on large molecules using molecular fragments. Preliminary investigation of ethyl chlorophyllide a and related molecules

Ab initio SCF calculations using the molecular fragment method are reported for four molecules related to chlorophyll a, i.e., free-base porphine, magnesium porphine, magnesium chlorin, and ethyl chlorophyllide a. Molecular orbital structure, the “four-orbital model”, reactivity sites, and Mg···N interactions are discussed.     

High magnetic shear gain in a liquid sodium stable Couette flow experiment: a prelude to an α-Ω dynamo

The Ω phase of the liquid sodium α-Ω dynamo experiment at New Mexico Institute of Mining and Technology in cooperation with Los Alamos National Laboratory has demonstrated a high toroidal field B(?) that is ?8×B(r), where B(r) is the radial component of an applied poloidal magnetic field. This enhanced toroidal field is produced by the rotational shear in stable Couette flow within liquid sodium at a magnetic Reynolds number Rm?120. Small turbulence in stable Taylor-Couette flow is caused by Ekman flow at the end walls, which causes an estimated turbulence energy fraction of (δv/v)(2)～10(-3).     

Reverse Osmosis Separations With Aromatic Polyamide Films and Hollow Fibers

When the ion exchange cellulose “Protion¹” was used on a pilot plant scale to produce a re-usable water from a proteinaceous treated meatworks effluent², it withstood such industrial handling without excessive degradation. A desire to exploit this characteristic of “Protion”, coupled with a wish to overcome problems like the blockage of downflow resin beds by fine suspended solids encountered in the meatworks effluent project, suggested using “Protion” in fluidised beds. However, since the introduction of batch fluidised bed processes seemed reasonably straightforward, it was decided instead to develop a truly continuous process in which “Protion” might have an even greater advantage over more fragile sorbents. Since continuous systems require a greater level of instrumentation and engineering skill than batch processes, it was later decided to apply the technique, not for effluent treatment but for the extraction of enzymes from protein broths It was thought that the greater product value in this type of system would better offset the higher instrumentation costs.     

Time and frequency resolved dynamics of ArBr2

We report the first spectroscopic observation of and vibrational predissociation dynamics for ArBr(2). Measurements are reported for the linear and T-shaped isomers with time and frequency resolution near the Fourier limit of a 15 ps pulse. For the T-shaped isomer, the Ar-Br(2) bond energy D(0) for the B state, nu(')=19, is found to be 200 cm(-1), yielding a D(0)(X) value of 213 cm(-1). Product appearance rates are determined for nu(')=16-25 of the B state of ArBr(2). While the rate generally increases with increasing vibrational quantum number, the trend is not monotonic. Also, obtaining reproducible rates for any given vibrational level requires very careful control of the experimental conditions. The data suggest that ArBr(2) undergoes vibrational predissociation (VP) in the sparse intramolecular vibrational relaxation regime. These observations are consistent with theoretical calculations that show that T-shaped ArBr(2) undergoes VP in the sparse regime, such that lifetimes are strongly dependent on both the vibrational and rotational quantum numbers. As for ArI(2), a linear isomer of ArBr(2) is found to contribute a quasicontinuous background to the excitation spectra. Direct excitation of this continuum results in a very broad product vibrational distribution.