High-precision frequency measurements: indispensable tools at the core of the molecular-level analysis of complex systems

This perspective article provides an assessment of the state-of-the-art in the molecular-resolution analysis of complex organic materials. These materials can be divided into biomolecules in complex mixtures (which are amenable to successful separation into unambiguously defined molecular fractions) and complex nonrepetitive materials (which cannot be purified in the conventional sense because they are even more intricate). Molecular-level analyses of these complex systems critically depend on the integrated use of high-performance separation, high-resolution organic structural spectroscopy and mathematical data treatment. At present, only high-precision frequency-derived data exhibit sufficient resolution to overcome the otherwise common and detrimental effects of intrinsic averaging, which deteriorate spectral resolution to the degree of bulk-level rather than molecular-resolution analysis. High-precision frequency measurements are integral to the two most influential organic structural spectroscopic methods for the investigation of complex materials—NMR spectroscopy (which provides unsurpassed detail on close-range molecular order) and FTICR mass spectrometry (which provides unrivalled resolution)—and they can be translated into isotope-specific molecular-resolution data of unprecedented significance and richness. The quality of this standalone de novo molecular-level resolution data is of unparalleled mechanistic relevance and is sufficient to fundamentally advance our understanding of the structures and functions of complex biomolecular mixtures and nonrepetitive complex materials, such as natural organic matter (NOM), aerosols, and soil, plant and microbial extracts, all of which are currently poorly amenable to meaningful target analysis. The discrete analytical volumetric pixel space that is presently available to describe complex systems (defined by NMR, FT mass spectrometry and separation technologies) is in the range of 108–14 voxels, and is therefore capable of providing the necessary detail for a meaningful molecular-level analysis of very complex mixtures. Nonrepetitive complex materials exhibit mass spectral signatures in which the signal intensity often follows the number of chemically feasible isomers. This suggests that even the most strongly resolved FTICR mass spectra of complex materials represent simplified (e.g. isomer-filtered) projections of structural space

APPLICATION OF FTICR MASS SPECTOMETRY FOR THE EVALUATION OF LIGHT EFFECT ON POLAR COMPOUNDS IN ITALIAN CRUDE OIL

The use of the crude oil as primary source of energy has significant social and environmental impacts, from accidents and routine activities such as seismic exploration, drilling, and generation of polluting wastes. Crude oil is subject to certain degradation processes: biotic and abiotic degradation. The fate of crude oil under UV and solar irradiation was studied. Compositions of the original and irradiated samples have been characterized by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR/MS) 7 T ThermoElectron that is capable of achieving the peak capacity needed to resolve individual components of a complex data matrix. Conversion of measured masses from the IUPAC mass scale (12C = 12.00000 Da) to the Kendrick mass scale (CH2=14.00000 instead of 14.01565 Da) was performed to facilitate identification of homologous series. The van Krevelen diagram was also used for a convenient visual separation of heteroatom class and alkylation pattern. Preliminary results shows the light influence on crude oil composition: our future work will be devoted to well understand the modification that sunlight irradiation induce on the nature of crude oil

Chemical and spectroscopic characterization of marine dissolved organic matter isolated using coupled reverse osmosis-electrodialysis

The coupled reverse osmosis-electrodialysis (RO/ED) method was used to isolate dissolved organic matter (DOM) from 16 seawater samples. The average yield of organic carbon was 75 ± 12%, which is consistently greater than the yields of organic carbon that have been commonly achieved using XAD resins, C18 adsorbents, and cross-flow ultrafiltration. UV-visible absorbance spectra and molar C/N ratios of isolated samples were consistent with the corresponding properties of DOM in the original seawater samples, indicating that DOM samples can be isolated using the coupled RO/ED method without any bias for/against these two properties. Five of the samples were desalted sufficiently that reliable measurements of their 13C and 1HNMR spectra and their Fourier transform ion cyclotron resonance (FTICR) mass spectra could be obtained. The 13C and 1HNMR spectra of RO/ED samples differed distinctly from those of samples that have been isolated in much lower yields by other methods. In particular, RO/ED samples contained a relatively lower proportion of carbohydrate carbon and a relatively greater proportion of alkyl carbon than samples that have been isolated using cross-flow ultrafiltration. From the FTICR mass spectra of RO/ED samples, samples from the open ocean contained a much lower proportion of unsaturated compounds and a much higher proportion of fatty acids than coastal samples.This material is based upon work supported by the National Science Foundation (NSF) under Grants No. 0425624 and 0425603.Peer Reviewe

The {\eta}'-carbon potential at low meson momenta

The production of $\eta^\prime$ mesons in coincidence with forward-going protons has been studied in photon-induced reactions on $^{12}$C and on a liquid hydrogen (LH$_2$) target for incoming photon energies of 1.3-2.6 GeV at the electron accelerator ELSA. The $\eta^\prime$ mesons have been identified via the $\eta^\prime\rightarrow \pi^0 \pi^0\eta \rightarrow 6 \gamma$ decay registered with the CBELSA/TAPS detector system. Coincident protons have been identified in the MiniTAPS BaF$_2$ array at polar angles of $2^{\circ} \le \theta _{p} \le 11^{\circ}$. Under these kinematic constraints the $\eta^\prime$ mesons are produced with relatively low kinetic energy ($\approx$ 150 MeV) since the coincident protons take over most of the momentum of the incident-photon beam. For the C-target this allows the determination of the real part of the $\eta^\prime$-carbon potential at low meson momenta by comparing with collision model calculations of the $\eta^\prime$ kinetic energy distribution and excitation function. Fitting the latter data for $\eta^\prime$ mesons going backwards in the center-of-mass system yields a potential depth of V = $-$(44 $\pm$ 16(stat)$\pm$15(syst)) MeV, consistent with earlier determinations of the potential depth in inclusive measurements for average $\eta^\prime$ momenta of $\approx$ 1.1 GeV/$c$. Within the experimental uncertainties, there is no indication of a momentum dependence of the $\eta^\prime$-carbon potential. The LH$_2$ data, taken as a reference to check the data analysis and the model calculations, provide differential and integral cross sections in good agreement with previous results for $\eta^\prime$ photoproduction off the free proton.Comment: 9 pages, 13 figures. arXiv admin note: text overlap with arXiv:1608.0607

Measurement of the Beam Asymmetry Σ\Sigma in the Forward Direction for pi0 Photoproduction

Photoproduction of neutral pions has been studied with the CBELSA/TAPS detector for photon energies between 0.92 and 1.68~GeV at the electron accelerator ELSA. The beam asymmetry~$\Sigma$ has been extracted for $115^\circ < \theta_{\rm c.m.} < 155^\circ$ of the $\pi^0$~meson and for $\theta_{\rm c.m.} < 60^\circ$. The new beam asymmetry data improve the world database for photon energies above 1.5~GeV and, by covering the very forward region, extend previously published data for the same reaction by our collaboration. The angular dependence of $\Sigma$ shows overall good agreement with the SAID parameterization.Comment: 11 pages, 10 figures, published in Phys. Rev. C, included LEPS data and MAID 2007 predictions for comparison with our dat

Photoproduction of {\omega} Mesons off the Proton

The differential cross sections and unpolarized spin-density matrix elements for the reaction $\gamma p\to p\omega$ were measured using the CBELSA/TAPS experiment for initial photon energies ranging from the reaction threshold to 2.5 GeV. These observables were measured from the radiative decay of the $\omega$ meson, $\omega\to\pi^0\gamma$. The cross sections cover the full angular range and show the full extent of the $t$-channel forward rise. The overall shape of the angular distributions in the differential cross sections and unpolarized spin-density matrix elements are in fair agreement with previous data. In addition, for the first time, a beam of linearly-polarized tagged photons in the energy range from 1150 MeV to 1650 MeV was used to extract polarized spin-density matrix elements. These data were included in the Bonn-Gatchina partial wave analysis (PWA). The dominant contribution to $\omega$ photoproduction near threshold was found to be the $3/2^+$ partial wave, which is primarily due to the sub-threshold $N(1720)\,3/2^+$ resonance. At higher energies, pomeron-exchange was found to dominate whereas $\pi$-exchange remained small. These $t$-channel contributions as well as further contributions from nucleon resonances were necessary to describe the entire dataset: the $1/2^-$, $3/2^-$, and $5/2^+$ partial waves were also found to contribute significantly.Comment: 8 pages, 5 figures, accepted for publication in Physics Letters

Photoproduction of meson pairs: First measurement of the polarization observable I^s

The polarization observable I^s, a feature exclusive to the acoplanar kinematics of multi-meson final states produced via linearly polarized photons, has been measured for the first time. Results for the reaction g p -> p pi0 eta are presented for incoming photon energies between 970 MeV and 1650 MeV along with the beam asymmetry I^c. The comparably large asymmetries demonstrate a high sensitivity of I^s to the dynamics of the reaction. Fits using Bonn-Gatchina partial wave analysis demonstrate that the new polarization observables carry significant information on the contributing partial waves.Comment: 11 pages, 6 figures, v2 to appear in Phys. Lett.

First measurement of the helicity asymmetry for γp→pπ0\gamma p\rightarrow p\pi^0 in the resonance region

The first measurement of the helicity dependence of the photoproduction cross section of single neutral pions off protons is reported for photon energies from 600 to 2300\,MeV, covering nearly the full solid angle. The data are compared to predictions from the SAID, MAID, and BnGa partial wave analyses. Strikingly large differences between data and predictions are observed which are traced to differences in the helicity amplitudes of well known and established resonances. Precise values for the helicity amplitudes of several resonances are reported

The N(1520) 3/2- helicity amplitudes from an energy-independent multipole analysis based on new polarization data on photoproduction of neutral pions

New data on the polarization observables T, P, and H for the reaction $\gamma p \to p\pi^0$ are reported. The results are extracted from azimuthal asymmetries when a transversely polarized butanol target and a linearly polarized photon beam are used. The data were taken at the Bonn electron stretcher accelerator ELSA using the CBELSA/TAPS detector. These and earlier data are used to perform a truncated energy-independent partial wave analysis in sliced-energy bins. This energy-independent analysis is compared to the results from energy-dependent partial wave analyses