Mutual Neutralization of NO

We have studied the mutual neutralization reaction of vibronically cold NO^{+} with O^{-} at a collision energy of ≈0.1 eV and under single-collision conditions. The reaction is completely dominated by production of three ground-state atomic fragments. We employ product-momentum analysis in the framework of a simple model, which assumes the anion acts only as an electron donor and the product neutral molecule acts as a free rotor, to conclude that the process occurs in a two-step mechanism via an intermediate Rydberg state of NO which subsequently fragments.

A localized view on molecular dissociation via electron-ion partial covariance.

Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d3/2 and 4d5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site.

Mutual neutralisation of O+ with O-: investigation of the role of metastable ions in a combined experimental and theoretical study.

The mutual neutralisation of O+ with O- has been studied in a double ion-beam storage ring with combined merged-beams, imaging and timing techniques. Branching ratios were measured at the collision energies of 55, 75 and 170 (± 15) meV, and found to be in good agreement with previous single-pass merged-beams experimental results at 7 meV collision energy. Several previously unidentified spectral features were found to correspond to mutual neutralisation channels of the first metastable state of the cation (O+(2Do), τ ≈ 3.6 hours), while no contributions from the second metastable state (O+(2Po), τ ≈ 5 seconds) were observed. Theoretical calculations were performed using the multi-channel Landau-Zener model combined with the anion centered asymptotic method, and gave good agreement with several experimentally observed channels, but could not describe well observed contributions from the O+(2Do) metastable state as well as channels involving the O(3s 5So) state.

Theoretical studies of infrared signatures of proton-bound amino acid dimers with homochiral and heterochiral moieties.

Proton-bound homochiral and heterochiral dimers, X-H+ -X, of five amino acids (X = Ser, Ala, Thr, Phe, and Arg) are investigated theoretically using quantum chemical density functional theory (DFT) calculations and molecular dynamics simulations with the aim to unveil diastereomer-specific mid-infrared (mid-IR) absorption bands in the spectral range of 1000 to 1800 cm-1 . The theoretical calculations performed in this work imply that all systems, except Ala2 H+ , have distinct mid-IR absorption bands in homochiral and heterochiral configurations, which make them appropriate systems to be studied experimentally with mid-IR spectroscopy. We show that intermolecular interaction with the side chain, in the form of hydrogen bonding or cation-π interaction, is necessary for chiral effects to be present in the mid-IR spectra of proton-bound dimers of amino acids. We also report new conformers for Ala2 H+ , Thr2 H+ , Phe2 H+ , and Arg2 H+ , which were not found in earlier studies of these dimers.

Dissociative recombination of H3+ and D5.

Compared with earlier years, the dissociative recombination of [Formula: see text] has not been very actively studied in recent years. New results from afterglow experiments are quoted and compared with results from ion storage rings and theory. New results for [Formula: see text] are discussed. This article also contains some historical remarks on hydrogen and its importance for the advancement of physics and chemistry. This article is part of a discussion meeting issue 'Advances in hydrogen molecular ions: H3+, H5+ and beyond'.

Evaluation of Sequential Processing for the Extraction of Starch, Lipids, and Proteins From Wheat Bran.

In line with the need to better utilize agricultural resources, and valorize underutilized fractions, we have developed protocols to increase the use of wheat bran, to improve utilization of this resource to additional products. Here, we report sequential processing for extraction of starch, lipids, and proteins from wheat brans with two different particle sizes leaving a rest-material enriched in dietary fiber. Mild water-based extraction of starch resulted in maximum 81.7 ± 0.67% yield. Supercritical fluid extraction of lipids by CO2 resulted in 55.2 ± 2.4% yield. This was lower than the corresponding yield using Soxhlet extraction, which was used as a reference method, but allowed a continued extraction sequence without denaturation of the proteins remaining in the raw-material. Alkaline extraction of non-degraded proteins resulted in a yield corresponding to one third of the total protein in the material, which was improved to reach 62 ± 8% by a combination of wheat bran enzymes activation followed by Osborne fractionation. The remaining proteins were extracted in degraded form, resulting in maximum 91.6 ± 1.6% yield of the total proteins content. The remaining material in both fine and coarse bran had a fiber content that on average corresponded to 73 ± 3%. The current work allows separation of several compounds, which is enabling valorization of the bran raw-material into several products.

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO2 , γ-Al2 O3 , CeO2 /SiO2 , Al2 O3 /SiO2 and TiO2 /SiO2.

Valeric acid is an important renewable platform chemical that can be produced efficiently from lignocellulosic biomass. Upgrading of valeric acid by catalytic pyrolysis has the potential to produce value added biofuels and chemicals on an industrial scale. Understanding the different mechanisms involved in the thermal transformations of valeric acid on the surface of nanometer-sized oxides is important for the development of efficient heterogeneously catalyzed pyrolytic conversion techniques. In this work, the thermal decomposition of valeric acid on the surface of nanoscale SiO2 , γ-Al2 O3 , CeO2 /SiO2 , Al2 O3 /SiO2 and TiO2 /SiO2 has been investigated by temperature-programmed desorption mass spectrometry (TPD MS). Fourier transform infrared spectroscopy (FTIR) has also been used to investigate the structure of valeric acid complexes on the oxide surfaces. Two main products of pyrolytic conversion were observed to be formed depending on the nano-catalyst used-dibutylketone and propylketene. Mechanisms of ketene and ketone formation from chemisorbed fragments of valeric acid are proposed and the kinetic parameters of the corresponding reactions were calculated. It was found that the activation energy of ketenization decreases in the order SiO2 >γ-Al2 O3 >TiO2 /SiO2 >Al2 O3 /SiO2 , and the activation energy of ketonization decreases in the order γ-Al2 O3 >CeO2 /SiO2 . Nano-oxide CeO2 /SiO2 was found to selectively catalyze the ketonization reaction.

Chirally sensitive collision induced dissociation of proton-bound diastereomeric complexes of tryptophan and 2-butanol.

In this work we report the stereo-dependent collision-induced dissociation (CID) of proton-bound complexes of tryptophan and 2-butanol. The dissociation efficiency was measured as a function of collision energy in single collision mode. The homochiral complex was found to be less stable against CID than a heterochiral one. Additional gas dependence measurements were performed with diastereomeric complexes that confirm the findings.

Experimental and theoretical XPS and NEXAFS studies of N-methylacetamide and N-methyltrifluoroacetamide.

Experimental Near-Edge X-ray Absorption Fine-Structure (NEXAFS) spectra of N-methyltrifluoroacetamide (FNMA), which is a peptide model system, measured at the C, N, O and F K-edges are reported. The features in the spectra have been assigned by Static-Exchange (STEX) calculations. Using the same method, we have also assigned previously measured NEXAFS spectra of another peptide model system, N-methylacetamide (NMA). To facilitate the NEXAFS feature assignments, X-ray Photoelectron Spectroscopy (XPS) measurements for NMA and FNMA have been carried out with the aim of obtaining the 1s electron ionization potentials, which are compared with the values predicted by our Hartree-Fock (ΔHF) and Multi Configuration Self Consistent Field (ΔMCSCF) calculations. We also demonstrate an approach to compensate for screening effects that are neglected in the STEX method. Ion yield measurements of FNMA associated with the excitation of several C, N, O, and F K-shell pre-edge resonances have revealed site-specific fragmentation in some cases which we interpret with the aid of our theoretical calculations.

Dimethylsilanone Generation from Pyrolysis of Polysiloxanes Filled with Nanosized Silica and Ceria/Silica.

Temperature-programmed desorption mass spectrometry (TPD MS) was used to study the pyrolysis of PDMS and its composites with nanosized silica and ceria/silica. The results suggest that the elusive organosilicon compound, dimethylsilanone, is generated from PDMS over a broad temperature range (in some cases starting at 70 °C). The presence of nano-oxides catalyzes this process. Ions characteristic of the fragmentation of dimethylsilanone under electron ionization are assigned with the aid of DFT structure calculations. Possible reaction mechanisms for dimethylsilanone generation are discussed in the context of the calculated kinetic parameters. Observed accompanying products of PDMS pyrolysis, such as tetramethylcyclodisiloxane and hexamethylcyclotrisiloxane, indicate that multiple channels are involved in the dimethylsilanone release.

Experimental studies of H13CO+ recombining with electrons at energies between 2-50,000 meV.

An investigation into the dissociative recombination process for H(13)CO(+) using merged ion-electron beam methods has been performed at the heavy ion storage ring CRYRING, Stockholm, Sweden. We have measured the branching fractions of the different product channels at ∼ 0 eV collision energy to be the following: CO + H 87 ± 2%, OH + C 9 ± 2%, and O + CH 4 ± 2%. The formation of electronically excited CO in the dominant reaction channel has also been studied, and we report the following tentative branching fractions for the different CO product electronic states: CO(X (1)Σ(+)) + H, 54 ± 10%; CO(a (3)Π) + H, 23 ± 4%; and CO(a' (3)Σ(+)) + H, 23 ± 4%. The absolute cross section between ∼ 2-50 000 meV was measured and showed resonance structures between 3 and 15 eV. The cross section was fitted in the energy range relevant to astrophysics, i.e., between 1 and 300 meV, and was found to follow the expression σ = 1.3 ± 0.3 × 10(-16) E(-1.29 ± 0.05) cm(2) and the corresponding thermal rate constant was determined to be k(T) = 2.0 ± 0.4 × 10(-7)(T/300)(-0.79 ± 0.05) cm(3) s(-1). Radioastronomical observations with the IRAM 30 m telescope of HCO(+) toward the Red Rectangle yielded an upper column density limit of 4 × 10(11) cm(-2) of HCO(+) at the 1σ level in that object, indicating that previous claims that the dissociative recombination of HCO(+) plays an important role in the production of excited CO molecules emitting the observed Cameron bands in that object are not supported.

Effective ligand passivation of Cu2O nanoparticles through solid-state treatment with mercaptopropionic acid.

In colloidal nanoparticle (NPs) devices, trap state densities at their surface exert a profound impact on the rate of charge carrier recombination and, consequently, on the deterioration of the device performance. Here, we report on the successful application of a ligand exchange strategy to effectively passivate the surface of cuprite (Cu2O) NPs. Cu2O NPs were prepared by means of a novel synthetic route based on flame spray pyrolysis. FTIR, XRD, XPS, and HRTEM measurements corroborate the formation of cubic cuprite Cu2O nanocrystals, excluding the possible presence of undesired CuO or Cu phases. Most importantly, steady-state emission and transient absorption assays document that surface passivation results in substantial changes in the intensity of emissive excitonic states--centered at copper and oxygen vacancies--and in the lifetime of excitons near the band edge. To shed light onto ultrafast processes in Cu2O nanocrystals additional pump probe experiments on the femtosecond and nanosecond time scales were carried out. Two discernible species were observed: on one hand, an ultrafast component (~ps) that relates to the excitons; on the other hand, a long-lived component (~µs) that originates from the defects/trap states.

Dissociative recombination of CH4(+).

CH4(+) is an important molecular ion in the astrochemistry of diffuse clouds, dense clouds, cometary comae, and planetary ionospheres. However, the rate of one of the common destruction mechanisms for molecular ions in these regions, dissociative recombination (DR), is somewhat uncertain. Here, we present absolute measurements for the DR of CH4(+) made using the heavy ion storage ring CRYRING in Stockholm, Sweden. From our collision-energy dependent cross-sections, we infer a thermal rate constant of k(Te) = 1.71(±0.02) × 10(­6)(Te/300)(−0.66(±0.02)) cm3 s(­1) over the region of electron temperatures 10 ≤ Te ≤ 1000 K. At low collision energies, we have measured the branching fractions of the DR products to be CH4 (0.00 ± 0.00); CH3 + H (0.18 ± 0.03); CH2 + 2H (0.51 ± 0.03); CH2 + H2 (0.06 ± 0.01); CH + H2 + H (0.23 ± 0.01); and CH + 2H2 (0.02 ± 0.01), indicating that two or more C­H bonds are broken in 80% of all collisions.

Dissociative recombination of H3+: 10 years in retrospect.

The dissociative recombination of H(3)(+) has been an intriguing problem for more than half a century. The early experiments on H(3)(+) during the first 20 years were carried out without mass analysis in decaying plasma afterglows, and thus the measured rates pertained to an uncontrolled mixture of H(3)(+) and impurity ions. When mass analysis was used, the rate coefficient was determined to be an uneventful value of about 10(-7) cm(3) s(-1), a very common rate coefficient for many molecular ions. But this was not the end of the story, not even the beginning of the end; it marked only the end of the beginning. The story I will tell in this article started about 10 years ago, when the dissociative recombination of H(3)(+) was approaching its deepest crisis. Today, owing to an extensive experimental and theoretical effort, the state of affairs has reached a historically unique level of harmony, although there still remains many things to sort out.

Brain responses to visceral stimuli reflect visceral sensitivity thresholds in patients with irritable bowel syndrome.

BACKGROUND & AIMS: Only a fraction of patients with irritable bowel syndrome (IBS) have increased perceptual sensitivity to rectal distension, indicating differences in processing and/or modulation of visceral afferent signals. We investigated the brain mechanisms of these perceptual differences. METHODS: We analyzed data from 44 women with IBS and 20 female healthy subjects (controls). IBS symptom severity was determined by a severity scoring system. Anxiety and depression symptoms were assessed using the hospital anxiety and depression score. Blood oxygen level-dependent signals were measured by functional magnetic resonance imaging during expectation and delivery of high (45 mmHg) and low (15 mmHg) intensity rectal distensions. Perception thresholds to rectal distension were determined in the scanner. Brain imaging data were compared among 18 normosensitive and 15 hypersensitive patients with IBS and 18 controls. Results were reported significant if peak P-values were ≤.05, with family-wise error correction in regions of interest. RESULTS: The subgroups of patients with IBS were similar in age, symptom duration, psychological symptoms, and IBS symptom severity. Although brain responses to distension were similar between normosensitive patients and controls, hypersensitive patients with IBS had greater activation of insula and reduced deactivation in pregenual anterior cingulate cortex during noxious rectal distensions, compared to controls and normosensitive patients with IBS. During expectation of rectal distension, normosensitive patients with IBS had more activation in right hippocampus than controls. CONCLUSIONS: Despite similarities in symptoms, hyper- and normosensitive patients with IBS differ in cerebral responses to standardized rectal distensions and their expectation, consistent with differences in ascending visceral afferent input.

Double-core-hole spectroscopy for chemical analysis with an intense X-ray femtosecond laser.

Theory predicts that double-core-hole (DCH) spectroscopy can provide a new powerful means of differentiating between similar chemical systems with a sensitivity not hitherto possible. Although DCH ionization on a single site in molecules was recently measured with double- and single-photon absorption, double-core holes with single vacancies on two different sites, allowing unambiguous chemical analysis, have remained elusive. Here we report that direct observation of double-core holes with single vacancies on two different sites produced via sequential two-photon absorption, using short, intense X-ray pulses from the Linac Coherent Light Source free-electron laser and compare it with theoretical modeling. The observation of DCH states, which exhibit a unique signature, and agreement with theory proves the feasibility of the method. Our findings exploit the ultrashort pulse duration of the free-electron laser to eject two core electrons on a time scale comparable to that of Auger decay and demonstrate possible future X-ray control of physical inner-shell processes.

GWAS findings for human iris patterns: associations with variants in genes that influence normal neuronal pattern development.

Human iris patterns are highly variable. The origins of this variation are of interest in the study of iris-related eye diseases and forensics, as well as from an embryological developmental perspective, with regard to their possible relationship to fundamental processes of neurodevelopment. We have performed genome-wide association scans on four iris characteristics (crypt frequency, furrow contractions, presence of peripupillary pigmented ring, and number of nevi) in three Australian samples of European descent. Both the discovery (n = 2121) and replication (n = 499 and 73) samples showed evidence for association between (1) crypt frequency and variants in the axonal guidance gene SEMA3A (p = 6.6 × 10(-11)), (2) furrow contractions and variants within the cytoskeleton gene TRAF3IP1 (p = 2.3 × 10(-12)), and (3) the pigmented ring and variants in the well-known pigmentation gene SLC24A4 (p = 7.6 × 10(-21)). These replicated findings individually accounted for around 1.5%-3% of the variance for these iris characteristics. Because both SEMA3A and TRAFIP1 are implicated in pathways that control neurogenesis, neural migration, and synaptogenesis, we also examined the evidence of enhancement among such genes, finding enrichment for crypts and furrows. These findings suggest that genes involved in normal neuronal pattern development may also influence tissue structures in the human iris.

Dissociative recombination of the acetaldehyde cation, CH(3)CHO(+).

The dissociative recombination of the acetaldehyde cation, CH(3)CHO(+), has been investigated at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. The dependence of the absolute cross section of the reaction on the relative kinetic energy has been determined and a thermal rate coefficient of k(T) = (1.5 ± 0.2) × 10(-6) (T/300)(-0.70±0.02) cm(3) s(-1) has been deduced, which is valid for electron temperatures between ∼10 and 1000 K. The branching fractions of the reaction were studied at ∼0 eV relative kinetic energy and we found that breaking one of the bonds between two of the heavy atoms occurs in 72 ± 2% of the reactions. In the remaining events the three heavy atoms stay in the same product fragment. While the branching fractions are fairly similar to the results from an earlier investigation into the dissociative recombination of the fully deuterated acetaldehyde cation, CD(3)CDO(+), the thermal rate coefficient is somewhat larger for CH(3)CHO(+). Astrochemical implications of the results are discussed.