Multidimensional separation prior to mass spectrometry: Getting closer to the bottom of the iceberg

While prefractionation has previously been shown to improve results in MS analysis, a novel combination provides an additional dimension of separation: protein fractionation by SDS-PAGE followed by IEF of tryptic peptides before separation by RP-LC [Atanassov and Urlaub, Proteomics 2013, 13, 2947-2955]. This three-step separation procedure prior to MS/MS substantially increases proteome coverage and represents a further step toward a more comprehensive analysis of complex proteomes

Positionally dependent ^(15)N fraction factors in the UV photolysis of N_2O determined by high resolution FTIR spectroscopy

Positionally dependent fractionation factors for the photolysis of isotopomers of N_2O in natural abundance have been determined by high resolution FTIR spectroscopy at three photolysis wavelengths. Fractionation factors show clear 15N position and photolysis wavelength dependence and are in qualitative agreement with theoretical models but are twice as large. The fractionation factors increase with photolysis wavelength from 193 to 211 nm, with the fractionation factors at 207.6 nm for ^(14)N^(15)N^916)O, ^(15)N^(14)N^(16)O and ^(14)N^(14)N^(18)O equal to −66.5±5‰,−27.1±6‰ and −49±10‰, respectively

Exploring the Origins of Deuterium Enrichments in Solar Nebular Organics

Deuterium-to-hydrogen (D/H) enrichments in molecular species provide clues about their original formation environment. The organic materials in primitive solar system bodies have generally higher D/H ratios and show greater D/H variation when compared to D/H in solar system water. We propose this difference arises at least in part due to 1) the availability of additional chemical fractionation pathways for organics beyond that for water, and 2) the higher volatility of key carbon reservoirs compared to oxygen. We test this hypothesis using detailed disk models, including a sophisticated, new disk ionization treatment with a low cosmic ray ionization rate, and find that disk chemistry leads to higher deuterium enrichment in organics compared to water, helped especially by fractionation via the precursors CH$_2$D$^+$/CH$_3^+$. We also find that the D/H ratio in individual species varies significantly depending on their particular formation pathways. For example, from $\sim20-40$ AU, CH$_4$ can reach $\rm{D/H\sim2\times10^{-3}}$, while D/H in CH$_3$OH remains locally unaltered. Finally, while the global organic D/H in our models can reproduce intermediately elevated D/H in the bulk hydrocarbon reservoir, our models are unable to reproduce the most deuterium-enriched organic materials in the solar system, and thus our model requires some inheritance from the cold interstellar medium from which the Sun formed.Comment: 11 pages, 7 figures, accepted for publication in Ap

Photochemical enrichment of deuterium in Titan's atmosphere: new insights from Cassini-Huygens

Cassini-Huygens data are used to re-examine the potential sources of the D/H enhancement over solar, measured in methane, in Titan's atmosphere. Assuming that the system is closed with respect to carbon, the use of constraints from the Huygens probe for the determination of the current mass of atmospheric methane and the most up-to-date determination of D/H from Cassini/CIRS infrared spectra allow us to show that photochemical enrichment of deuterium is not sufficient to be the sole mechanism yielding the measured D/H value. A possible fractionation between CH3D and CH4 during the escape process may slightly enhance the deuterium enrichment, but is not sufficient to explain the observed D/H value over the range of escape values proposed in the literature. Hence, alternative mechanisms such as a primordial deuterium enrichment must be combined with the photochemical enrichment in Titan's atmosphere in order to explain its current D/H value.Comment: 4 pages, 3 figures, accepted in ApJ

Carbon Fractionation in PDRs

We upgraded the chemical network from the UMIST Database for Astrochemistry 2006 to include isotopes such as ^{13}C and ^{18}O. This includes all corresponding isotopologues, their chemical reactions and the properly scaled reaction rate coefficients. We study the fractionation behavior of astrochemically relevant species over a wide range of model parameters, relevant for modelling of photo-dissociation regions (PDRs). We separately analyze the fractionation of the local abundances, fractionation of the total column densities, and fractionation visible in the emission line ratios. We find that strong C^+ fractionation is possible in cool C^+ gas. Optical thickness as well as excitation effects produce intensity ratios between 40 and 400. The fractionation of CO in PDRs is significantly different from the diffuse interstellar medium. PDR model results never show a fractionation ratio of the CO column density larger than the elemental ratio. Isotope-selective photo-dissociation is always dominated by the isotope-selective chemistry in dense PDR gas. The fractionation of C, CH, CH^+, and HCO^+ is studied in detail, showing that the fractionation of C, CH and CH^+ is dominated by the fractionation of their parental species. The light hydrides chemically derive from C^+, and, consequently, their fractionation state is coupled to that of C^+. The fractionation of C is a mixed case depending on whether formation from CO or HCO^+ dominates. Ratios of the emission lines of [C II], [C I], ^{13}CO, and H^{13}CO^+ provide individual diagnostics to the fractionation status of C^+, C, and CO.Comment: to be published in A&