Acetone cation chemistry under varying electron density conditions: from unimolecular decomposition to dissociative recombination processes

The chemistry of ionized acetone:Ar mixtures under varied ionizing electron density conditions has been studied using matrix‐isolation techniques. Gaseous acetone diluted in excess argon gas was subjected to electron bombardment with 300 eV electrons at currents between 20 and 200 μA. Linear wire ‘pin’ and metal ‘plate’ electron collector geometries were employed, allowing a wide range of electron density conditions to be explored. The products of subsequent reaction processes were matrix isolated and analyzed by Fourier transform infrared absorption spectroscopy. Products included methane, ketene, 1‐propen‐2‐ol (the enol isomer of acetone), CO, HCO, ethane, ethane, acetylene and CCCO. Product absolute and relative yields varied with acetone number density, the choice of anode geometry and the rate of electron bombardment. The overall chemistry observed is rationalized in terms of mechanistic steps involving unimolecular cation decomposition, ion–molecule reactions, radical–radical reactions and dissociative recombination processes. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization of the Reaction of Chloroacetaldehyde with Single and Double Stranded DNA

Chloroacetaldehyde reacts with viral M13mp18 single and double stranded DNA to form the highly fluorescent adducts, etheno-AMP and etheno-CMP.

Absorbance and fluorescence spectroscopy can be used to monitor and characterize these reactions. Both single and double stranded DNA showed increases in the absorbance following reaction with the aldehyde. The fluorescence also increased in these two groups and continued to rise with increasing time of incubation until a point of saturation was reached. The fluorescence of the double stranded moiety was considerably enhanced following reaction with the aldehyde while that of the single stranded population was not, making this method appropriate for the separation of small quantities of the two populations of DNA.     

ALP production through non-linear Compton scattering in intense fields

We derive production yields for massive pseudo-scalar and scalar axion-like-particles (ALPs), through non-linear Compton scattering of an electron in the background of low- and high-intensity electromagnetic fields. In particular, we focus on electromagnetic fields from Gaussian plane wave laser pulses. A detailed study of the angular distributions and effects of the scalar and pseudo-scalar masses is presented. It is shown that ultra-relativistic seed electrons can be used to produce scalars and pseudo-scalars with masses up to the order of the electron mass. We briefly discuss future applications of this work towards lab-based searches for light beyond-the-Standard-Model particles.     

Syntheses,Structures and Photoelectron Spectra of Phospha-Alkenes and Phospha-Alkynes and Their Transition Metal Complexes

Abstract

The chemistry of the novel phospha-alkenes RP[dbnd]CR'₂, and phospha-alkynes, RC[tbnd]P, containing 2pπ-3pπ bonds is of current interest.^1,2 Recent molecular orbital calculations,^3,4 suggest that the highest occupied molecular orbital in CH₂[dbnd]PH is of the π-type with the phosphorus lone pair ó-orbital only slightly more stable while the π? lumo orbital is relatively low lying. We now report He (I) photoelectron spectroscopic studies on a variety of RC[tbnd]P molecules^5,6 which indicate that the homo is also of the π-type and the π-σ separation is much greater than that found in the analogous RC[tbnd]N systems.     

An Efficient Synthesis of 15N-Hydroxyurea

Treatment of trimethylsilyl isocyanate with ¹⁵N-hydroxylamine hydrochloride produces ¹⁵N-hydroxyurea, a valuable pharmacological tool, in an efficient, one-pot procedure in 74% yield. Recrystallization of the crude product yields analytically pure material in 47% overall yield.     

Behaviour of polycyclic aromatic hydrocarbons in dissolved,colloidal, and particulate phases in sedimentary cores

Solid-phase microextraction (SPME) has been successfully used for extracting polycyclic aromatic hydrocarbons (PAHs) from porewater samples from the Mersey Estuary, UK. The majority of the PAHs in porewater samples are associated with colloids due to the high DOC concentrations. The truly dissolved PAH concentrations varied from 66 to 1050?ng?L^?1 in core 2 and from 95 to 740?ng?L^?1 in core 3, and were dominated by naphthalene, fluoranthene, and pyrene. Although absent in the dissolved phase, the high-molecular-mass compounds were found in the colloid-associated fraction of porewater. PAHs in sediments arose from a range of compounds with 4- and 5-ring PAHs dominating. The partitioning of PAHs between sediment and porewater shows that PAHs are enriched in the sediment phase. When the soot carbon content was considered, predictions of the partition behaviour were found to agree more closely with the observed distribution. The results reiterate the importance of evaluating the speciation of organic pollutants in both porewater and sediments in order to accurately predict their environmental fate and potential toxicity.