Synthesis of Unprotected Carboxy Indazoles via Pd-Catalyzed Carbonylation

The first published synthesis of unprotected carboxy indazoles from the corresponding bromoindazoles is described. This is achieved via Pd(II)-catalyzed carbonylation and is demonstrated to work on a variety of indazoles.     

Developments in plasma source/mass spectrometry

The field of plasma source/mass spectrometry is critically reviewed and its current status assessed. An overview of PS/MS applications is provided and a discussion is offered of key problem areas that currently exist in the field. Areas that are now receiving strong research attention are outlined and a view is offered for future prospects of plasma source/mass spectrometry as a technique for the determination of elements.     

Noncritically phase-matched fourth harmonic generation of Nd:glass lasers in partially deuterated KDP crystals

Noncritically phase-matched (NCPM) fourth harmonic generation (FHG) of Nd:glass laser radiation in partially deuterated dihydrogen phosphate (KD*P) crystals has been demonstrated. At an Nd:glass laser wavelength of 1053.0 nm, NCPM FHG is achieved in 70% deuterated KD*P at a crystal temperature of 18.5±0.1 °C. Tuning the fundamental laser wavelength from 1052.9 to 1053.2 nm, FHG in KD*P is NCPM by changing the crystal temperature from 17.9 °C to 20.5 °C. When driven with 2.4 J of second harmonic radiation in a 3 ns flat-top pulse, corresponding to 1 GW/cm(2) 2ω drive intensity, 1.9 J of fourth harmonic radiation was generated in a 6 mm long KD*P crystal, yielding a second to fourth harmonic energy conversion efficiency of 79%.     

Modelling the erosion efficiency of cavitation cleaning jets

A model is presented of the erosion damage and cleaning efficiency of cavitation and conventional cleaning jets. The effect of supply pressure, jet velocity, standoff distance, nozzle diameter and type of fluid are considered and assessed in relation to experimental findings.     

Spectral theory for general nonautonomous/random dispersal evolution operators

We investigate the spectral theory of the following general nonautonomous evolution equation

     

Diastereoselective synthesis of quaternary alpha-amino acids from diketopiperazine templates

Sequential enolate alkylations of (S)-N(1)-methyl-5-methoxy-6-isopropyl-3,6-dihydropyrazin-2-one and (S)-N(1)-p-methoxybenzyl-5-methoxy-6-isopropyl-3,6-dihydropyrazin-2-one proceed with excellent levels of diastereoselectivity (>90% de) affording quaternary alpha-amino acids in high enantiomeric excess (>98% ee) after deprotection and hydrolysis.     

Toward the computational design of diastereomeric resolving agents: an experimental and computational study of 1-phenylethylammonium-2-phenylacetate derivatives

The crystal structures, including two new polymorphs, of three diastereomerically related salt pairs formed by (R)-1-phenylethylammonium (1) with (S&R)-2-phenylpropanoate (2), (S&R)-2-phenylbutyrate (3), and (S&R)-mandelate (4) ions were characterized by low-temperature single crystal or powder X-ray diffraction. Thermal, solubility, and solution calorimetry measurements were used to determine the relative stabilities of the salt pairs and polymorphs. These were qualitatively predicted by lattice energy calculations combining realistic models for the dominant intermolecular electrostatic interactions and ab initio calculations for the ions' conformational energies due to the distortion of their geometries by the crystal packing forces. Crystal structure prediction studies were also performed for the highly polymorphic diastereomeric salt pair (R)-1-phenylethylammonium-(S&R)-2-phenylbutyrate (1-3) in an attempt to predict the separation efficiency without relying on experimental information. This joint experimental and computational investigation provides a stringent test for the reliability of lattice modeling approaches to explain the origins of chiral resolution via diastereomer formation (Pasteurian resolution). The further developments required for the computational screening of single-enantiomer resolving agents to achieve optimal chiral separation are discussed.     

Quantification routines for adsorption studies in static secondary ion mass spectrometry and the effect of ionisation probability

It is shown that the usual method of quantification of surface composition in static secondary ion mass spectrometry (SSIMS), which is purely comparative in nature, is unsuitable for adsorption studies by SSIMS. This is because of the effect of the ionisation efficiency and ion stability of a particular ion produced from a molecule adsorbed on the surface of a substrate. The established routine results in a non-linear relationship between calculated relative surface coverage and the ion selected to characterise the adsorbate. The application of a new normalisation routine to time-of-flight secondary ion mass spectrometry (ToF-SIMS) data has been used to account for this discrepancy, and also takes into account the effect of a possible contribution from the clean substrate to the ion selected to characterise the adsorbate molecule. This routine is suggested only for use with organic secondary ions, where the ionisation potential of such ions is of a comparable magnitude, and should prove particularly useful in the application of surface analysis techniques to adsorption studies.