Short-lived radical characterisation: novel radical trap synthesis, application and methodology development

Radical intermediates play a key role in many chemical processes. However, existing methods for their characterisation have flaws that limit mechanistic and kinetic understanding of these processes, especially for short-lived radicals. A new radical characterisation technique was developed which used novel radical traps, consisting of an allyl group attached to a leaving group, which formed a stable radical upon cleavage. Reaction of a radical with novel radical trap formed a stable radical and non-radical product containing the reactant radical, which was then characterised by conventional techniques, such as NMR spectroscopy and MS. Novel radical trapping was used to successfully detect and characterise a diverse array of short-lived and long-lived radical intermediates across a wide range of radical reactions, including synthetic, biochemical and atmospheric radical reactions, offering valuable mechanistic and kinetic insights. Experiments indicated that novel radical trapping did not lead to false positives, in contrast to most existing short-lived radical characterisation techniques. Full characterisation of an isolated trapped phenylthiyl radical confirmed the trapping mechanism occurred as expected. Novel radical trapping indicated the radical resting state for different substrates in Ru-photocatalysed radical thiol-ene addition and enabled an initiation mechanism to be hypothesised for catalyst-free photoinitiated radical dearomative spirocyclisation. The antioxidant activity of ascorbic acid was probed using aqueous novel radical trapping. Observations from novel radical trapping of gaseous α-pinene ozonolysis offered validation to mechanisms hypothesised but not widely accepted in literature. Detection limits of gaseous [RO2●] using novel radical trapping were estimated to be >1×10^9 molec. cm^-3 (S/N = ~2, 10 min), which would be suitable for some atmospheric field measurements. These investigations demonstrated the viability of novel radical trapping as a tool to investigate any radical reaction. It is hoped that chemists will widely adopt this technique to improve understanding and aid development of reactions involving radical intermediates

Structural role of the tyrosine residues of cytochrome c

The tertiary structures of horse, tuna, Neurospora crassa, horse [Hse65,Leu67]- and horse [Hse65,Leu74]-cytochromes c were studied with high-resolution 1H n.m.r. spectroscopy. The amino acid sequences of these proteins differ at position 46, which is occupied by phenylalanine in the horse proteins but by tyrosine in the remaining two, and at positions 67, 74 and 97, which are all occupied by tyrosine residues in horse and tuna cytochrome c but in the other proteins are substituted by phenylalanine or leucine, though there is only one such substitution per protein. The various aromatic-amino-acid substitutions do not seriously affect the protein structure

Primary Beam Shape Calibration from Mosaicked, Interferometric Observations

Image quality in mosaicked observations from interferometric radio telescopes is strongly dependent on the accuracy with which the antenna primary beam is calibrated. The next generation of radio telescope arrays such as the Allen Telescope Array (ATA) and the Square Kilometer Array (SKA) have key science goals that involve making large mosaicked observations filled with bright point sources. We present a new method for calibrating the shape of the telescope's mean primary beam that uses the multiple redundant observations of these bright sources in the mosaic. The method has an analytical solution for simple Gaussian beam shapes but can also be applied to more complex beam shapes through $\chi^2$ minimization. One major benefit of this simple, conceptually clean method is that it makes use of the science data for calibration purposes, thus saving telescope time and improving accuracy through simultaneous calibration and observation. We apply the method both to 1.43 GHz data taken during the ATA Twenty Centimeter Survey (ATATS) and to 3.14 GHz data taken during the ATA's Pi Gigahertz Sky Survey (PiGSS). We find that the beam's calculated full width at half maximum (FWHM) values are consistent with the theoretical values, the values measured by several independent methods, and the values from the simulation we use to demonstrate the effectiveness of our method on data from future telescopes such as the expanded ATA and the SKA. These results are preliminary, and can be expanded upon by fitting more complex beam shapes. We also investigate, by way of a simulation, the dependence of the accuracy of the telescope's FWHM on antenna number. We find that the uncertainty returned by our fitting method is inversely proportional to the number of antennas in the array.Comment: Accepted by PASP. 8 pages, 8 figure

Discrete wetland groundwater discharges revealed with a three-dimensional temperature model and botanical indicators (Boxford, UK)

Wetlands provide unique goods and services, as habitats of high biodiversity. Hydrology is the principal control on wetland functioning; hence, understanding the water source is fundamental. However, groundwater inflows may be discrete and easily missed. Research techniques are required with low cost and minimal impact in sensitive settings. In this study, the effectiveness of using a three-dimensional (3D) temperature model and botanical indicators to characterise groundwater discharge is explored at the CEH (Centre for Ecology and Hydrology) River Lambourn Observatory, Boxford, UK. This comprises a 10 ha lowland riparian wetland, designated for its scientific interest and conservation value. Temperature data were collected in winter at multiple depths down to 0.9 m over approximately 3.6 ha and transformed into a 3D model via ordinary kriging. Anomalous warm zones indicated distinct areas of groundwater upwelling which were concurrent with relic channel structures. Lateral heat propagation from the channels was minimal and restricted to within 5–10 m. Vertical temperature sections within the channels suggest varying degrees of groundwater discharge along their length. Hydrochemical analysis showed that warmer peat waters were akin to deeper aquifer waters, confirming the temperature anomalies as areas of groundwater discharge. Subsequently, a targeted vegetation survey identified Carex paniculata as an indicator of groundwater discharge. The upwelling groundwater contains high concentrations of nitrate which is considered to support the spatially restricted growth of Carex paniculata against a background of poor fen communities located in reducing higher-phosphate waters

Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions

Two applications of a radical trap based on a homolytic substitution reaction (SH2') are presented for the trapping of short-lived radical intermediates in organic reactions. The first example is a photochemical cyanomethylation catalyzed by a Ru complex. Two intermediate radicals in the radical chain propagation have been trapped and detected using mass spectrometry (MS), along with the starting materials, products and catalyst degradation fragments. Although qualitative, these results helped to elucidate the reaction mechanism. In the second example, the trapping method was applied to study the radical initiation catalyzed by a triethylboronoxygen mixture. In this case, the concentration of trapped radicals was sufficiently high to enable their detection by nuclear magnetic resonance (NMR). Quantitative measurements made it possible to characterize the radical flux in the system under different reaction conditions (including variations of solvent, temperature and concentration) where modelling was complicated by chain reactions and heterogeneous mass transfer

Atom gravimeters and gravitational redshift

In a recent paper, H. Mueller, A. Peters and S. Chu [A precision measurement of the gravitational redshift by the interference of matter waves, Nature 463, 926-929 (2010)] argued that atom interferometry experiments published a decade ago did in fact measure the gravitational redshift on the quantum clock operating at the very high Compton frequency associated with the rest mass of the Caesium atom. In the present Communication we show that this interpretation is incorrect.Comment: 2 pages, Brief Communication appeared in Nature (2 September 2010